ORNL/TM-2010/326

Intermediate Ethanol Blends 

Infrastructure Materials Compatibility 

Study: Elastomers, Metals, and Sealants 

March 2011 

Prepared by 

M. D. Kass 

T. J. Theiss 

C. J. Janke 

S. J. Pawel 

S. A. Lewis 
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ORNL/TM-2010/326 

Energy and Transportation Science Division 

INTERMEDIATE ETHANOL BLENDS INFRASTRUCTURE MATERIALS 

COMPATIBILITY STUDY: ELASTOMERS, METALS, AND SEALANTS 

Michael D. Kass 

Timothy J. Theiss 

Christopher J. Janke 

Steven J. Pawel 

Samuel A. Lewis 

Date Published: March 2011 

Prepared by 

OAK RIDGE NATIONAL LABORATORY 

Oak Ridge, Tennessee 37831-6283 

managed by 

UT-BATTELLE, LLC 

for the 

U.S. DEPARTMENT OF ENERGY 

under contract DE-AC05-00OR22725 

iii 

CONTENTS 

Page 

LIST OF FIGURES ....................................................................................................................................... v

LIST OF TABLES ...................................................................................................................................... vii

ACRONYMS ............................................................................................................................................... ix

FOREWORD ............................................................................................................................................... xi

ACKNOWLEDGMENTS ..........................................................................................................................xiii

EXECUTIVE SUMMARY ......................................................................................................................... xv

1. INTRODUCTION ................................................................................................................................. 1

1.1 ETHANOL USE AS A TRANSPORTATION FUEL ................................................................ 1

2. LITERATURE REVIEW OF ELASTOMER COMPATIBILITY WITH ETHANOL-BLENDED 

GASOLINE ........................................................................................................................................... 5

2.1 REVIEW OF DOE ETHANOL MATERIAL COMPATIBILITY STUDIES ......................... 12

2.1.1 ORNL Dispenser Study Using CE25a and CE85a .................................................... 12

2.1.2 ORNL CE20a Compatibility Study of Fluorocarbons and Metals ............................ 13

3. ORNL FUEL DISPENSER INFRASTRUCTURE MATERIALS STUDY: METALS, 

ELASTOMERS, AND SEALANTS ................................................................................................... 14

3.1 MATERIALS AND SPECIMEN PREPARATION ................................................................. 15

3.1.1 Metals and Alloys ...................................................................................................... 16

3.1.2 Elastomers ................................................................................................................. 18

3.1.3 Sealants ...................................................................................................................... 19

3.2 EXPOSURE PROTOCOL ........................................................................................................ 19

3.3 ANALYTICAL METHODS ..................................................................................................... 20

3.3.1 Sealants ...................................................................................................................... 21

3.3.2 Test Fuels .................................................................................................................. 23

4. RESULTS ............................................................................................................................................ 24

4.1 PERFORMANCE OF STIR CHAMBERS .............................................................................. 24

4.2 SPECIMEN ANALYSIS OVERVIEW .................................................................................... 24

4.3 METAL COMPATIBILITY PERFORMANCE ...................................................................... 24

4.4 ELASTOMER COMPATIBILITY PERFORMANCE ............................................................ 28

4.4.1 Fluid (Liquid) Exposures ........................................................................................... 28

4.4.2 Vapor Exposures ....................................................................................................... 38

4.5 SEALANT COMPATIBILITY PERFORMANCE .................................................................. 40

5. CONCLUSIONS ................................................................................................................................. 40

5.1 METALS AND ALLOYS ........................................................................................................ 40

5.2 ELASTOMERS ........................................................................................................................ 40

5.2.1 Fluorocarbons ............................................................................................................ 42

5.2.2 Fluorosilicone Rubber ............................................................................................... 42

5.2.3 Silicone Rubber ......................................................................................................... 42
iv 

5.2.4 SBR ........................................................................................................................... 42

5.2.5 NBR ........................................................................................................................... 42

5.2.6 Polyurethane .............................................................................................................. 43

5.2.7 Neoprene ................................................................................................................... 43

5.3 Vapor-Exposed Specimens ....................................................................................................... 43

5.4 Sealants ..................................................................................................................................... 43

6. REFERENCES .................................................................................................................................... 44

APPENDIX A. ORNL/UL POSTMORTEM ANALYSIS OF FACEPLATE RUBBER-CORK 

GASKETS USED IN NREL/UL DISPENSERS 1, 3, AND 5 ....................................... A-1 

APPENDIX B. ORNL DISPENSER STUDY USING RECIRCULATING CE25A 

AND CE85A TEST FLUIDS .......................................................................................... B-1 

APPENDIX C. COMPATIBILITY ASSESSMENT OF FUEL DISPENSER METALS AND 

ELASTOMERS IN AN AGGRESSIVE E20 FUEL ...................................................... C-1 

APPENDIX D. TABULATED DMA RESULTS .................................................................................... D-1 
v 

LIST OF FIGURES 

Figure Page 

 1 Influence of conductivity with ethanol concentration of gasoline (reprinted with 

permission) ................................................................................................................................ 2

 2 Influence of conductivity as a function of ethanol and water content (reprinted with 

permission) ................................................................................................................................ 3 

 3 Total Hansen Solubility Parameter as a function of ethanol concentration ............................... 4

 4 Volume swell results for selected elastomers for different test fuels ........................................ 8

 5 Decline in hardness for selected elastomers for different test fuels ........................................... 9

 6 Percent change in volume for selected elastomers exposed to Fuel C, CE10a, 

and CE20 ................................................................................................................................. 10

 7 Experimental stir chamber ....................................................................................................... 13

 8 Schematic showing dispenser materials and components from the delivery truck 

to the UST ................................................................................................................................ 14

 9 Schematic showing dispenser materials and components from the UST to the nozzle ........... 15

 10 Representative pre-test appearance of plated coupons after a portion of the plating 

had been removed to expose the substrate ............................................................................... 16

 11 Mounted specimens and mounting bracket ............................................................................. 17

 12 Thread with applied sealant and the test fixture with three mounted specimens ..................... 19

 13 Schematic representation of dynamic stir chamber ................................................................. 20

 14 Typical DMA plot of storage modulus with temperature ........................................................ 22

 15 Schematic of sealant test protocol ........................................................................................... 22

 16 Post-exposure appearance of the cartridge brass specimens following 28 days of 

exposure to vapor (~55°C) and liquid (60°C) in the indicated environments ......................... 26

 17 Post-exposure appearance of the phosphor bronze specimens following 28 days of 

exposure to vapor (~55°C) and liquid (60°C) in the indicated environments ......................... 26

 18 Post-exposure appearance of the galvanized steel specimens following 28 days of 

exposure to vapor (~55°C) and liquid (60°C) in the indicated environments ......................... 27

 19 XPS results for cartridge brass following immersion in CE25a for 28 days at 60°C .............. 27

 20 Post-exposure appearance of the chromium-plated brass specimens following 28 days 

of immersion in the indicated environments ............................................................................ 29

 21 Decrease in hardness as a function of volume swell and ethanol concentration for 

each elastomer type evaluated ................................................................................................. 30

 22 Mass change of elastomers after drying compared to the initial baseline condition as 

function of volume swell and test fluid ................................................................................... 31

 23 Dry volume change of elastomers compared to the initial baseline condition as a 

function of volume swell and fuel type ................................................................................... 32

 24 Correlation between dry volume change and dry mass change ............................................... 32

 25 Change in hardness (after drying at 60°C for 20 hr as a function of the change in 

dry mass) .................................................................................................................................. 33

 26 Change in hardness (after drying at 60°C for 20 hr as a function of the change in 

dry volume) .............................................................................................................................. 34

 27 Change in onset storage modulus as a function of dry mass change ....................................... 35

 28 Correlation of the change in hardness and the storage modulus when measured 

at 25°C ..................................................................................................................................... 36

 29 Percent change in the storage modulus at 25°C for each elastomer sample ............................ 37

 30 Shift in the onset glass transition temperature Tg from the initial baseline condition ............. 37

 31 Point change in hardness comparison between vapor- and fluid-exposed specimens ............. 38
vi 

 32 Shift in Tg comparison between vapor- and fluid-exposed specimens .................................... 39

 33 Shift in storage modulus at 25oC comparison between vapor- and fluid-exposed 

specimens ................................................................................................................................. 39

 34 Sealant test results .................................................................................................................... 40

 A-1 Housing gasket for Dispenser 3 (used), which passed the UL 87a tests ................................ A-4

 A-2 Faceplate gasket for Dispenser 1 (new), which failed the UL 87a tests ................................ A-4

 A-3 Faceplate gasket for Dispenser 5 (used), which failed the UL 87a tests ............................... A-5

 A-4 TGA (in air) curves for rubber-cork gaskets used in Dispensers 1, 3, and 5 ......................... A-6

 B-1 Photograph showing assembled and operating dispensers .................................................... B-4

 B-2 Schematic diagram showing the arrangement of the dispenser components ......................... B-5

 B-3 Temperature profile for the CE25a dispenser during the first 15 week evaluation 

period ..................................................................................................................................... B-6

 B-4 Photograph showing the change in appearance (color) of the fuel types during the 

first (summer) 15 week exposure period ............................................................................... B-7

 B-5 Temperature profile for the CE25a dispenser during the second 15 week evaluation 

period ..................................................................................................................................... B-8

 B-6 Photograph showing the change in appearance (color) of the fuel types during the 

second 15 week exposure period ........................................................................................... B-8

 C-1 Schematic representation of one stir tank assembly including temperature control .............. C-4

 C-2 Representative temperature profile of the stir tanks during th entire test period ................... C-7

 C-3 Composition of Fuel C in the headspace and in the fluid for each exposure period ............. C-8

 C-4 Composition of CE20a in the headspace and in the fluid for each exposure period ............. C-8

 C-5 Photograph showing discoloration associated with brass and bronze specimens 

exposed to (a) Fuel C headspace, (b) between 12 and 16 weeks in CE20a, and (c) 0 to 

16 weeks in CE20a .............................................................................................................. C-10

 C-6 Photograph showing discoloration associated with terne-plated and galvanized steels 

exposed to (a) Fuel C headspace, (b) between 12 and 16 weeks in CE20a, and (c) 0 to 

16 weeks in CE20a .............................................................................................................. C-10

 C-7 Modulus of VitonTM elastomers measured for the original condition, thermally aged 

for 4 weeks at 60°C, and selected exposures at 60°C to (a) Fuel C and (b) CE20a ............ C-11

 C-8 Modulus100 of DyneonTM elastomers measured for the original condition, thermally 

aged for 4 weeks at 60°C, and selected exposures at 60°C to (a) Fuel C and (b)

CE20a .................................................................................................................................. C-12

 C-9 Tensile strength of NBR and Viton elastomers measured for the original condition, 

thermally aged for 4 weeks at 60°C, and selected exposures at 60°C to (a) Fuel C and 

(b) CE20a ............................................................................................................................. C-13

 C-10 Tensile strength of NBR and Dyneon elastomers measured for the original condition, 

thermally aged for 4 weeks at 60°C, and selected exposures at 60°C to (a) Fuel C and 

(b) CE20a ............................................................................................................................. C-14

 C-11 Shore A hardness measurements of NBR and Viton elastomers measured for the 

original condition, thermally aged for 4 weeks at 60°C, and selected exposures at 

60°C to (a) Fuel C and (b) CE20a ....................................................................................... C-15

 C-12 Shore A hardness measurements of NBR and DyneonTM elastomers measured for the 

original condition, thermally aged for 4 weeks at 60°C, and selected exposures at 

60°C to (a) Fuel C and (b) CE20a ....................................................................................... C-16

 C-13 Volume increase of elastomer specimens measured for the original condition, 

thermally aged for 4 weeks at 60°C, and selected exposures at 60°C to (a) Fuel C and 

(b) CE20a ............................................................................................................................. C-18
vii 

LIST OF TABLES 

Table Page 

 1 Rubber types used in this study ................................................................................................. 5

 2 Standard compatibility rating system ........................................................................................ 5 

 3 Key properties of isooctane, toluene, and ethanol associated with fluid-elastomer 

compatibility .............................................................................................................................. 6

 4 Test fuel and elastomer type listing for key references ............................................................. 7

 5 Metal and alloy specimen listing ............................................................................................. 17

 6 Aggressive ethanol formulation ............................................................................................... 23

 7 Annualized corrosion rates of phosphor bronze ...................................................................... 25

 8 Parker elastomer compatibility rating for o-ring applications ................................................. 29

 A-1 Thickness of the rubber-cork gaskets used as meter seals ..................................................... A-3 

 B-1 Timeline for fuel sample withdrawal ..................................................................................... B-6

 C-1 Formulation to make 1.0 liter of aggressive ethanol............................................................. C-4

 C-2 List of metal and elastomer coupon materials ....................................................................... C-5

 C-3 Specimen removal and insertion protocol ............................................................................. C-6

 C-4 Average headspace gas temperature (°C) for each of the three exposure periods ................. C-7

 C-5 Mass loss of brass, bronze, terne-plated steel, and galvanized steel specimens 

exposed to CE20a fuel ........................................................................................................... C-9

 D-1 DMA results for elastomer specimens ................................................................................... D-3

 D-2 DMA results for NBR specimens .......................................................................................... D-4

 D-3 DMA results for non-fluorocarbons and non-NBRs .............................................................. D-5

ix 

ACRONYMS 

ACN Acrylonitrile 

ASTM American Society for Testing and Materials 

API American Petroleum Institute 

CRC Coordinating Research Council 

DOE Department of Energy 

DMA Dynamic Mechanical Analysis 

E’ Storage modulus 

E’25 Storage modulus at 25o

C 

E25 Gasoline containing 25% ethanol by volume 

E85 Gasoline containing 85% ethanol by volume 

EISA Energy Independence and Security Act 

EPA U. S. Environmental Protection Agency 

FFV Flex-Fuel Vehicle 

GC-MS Gas chromatography–mass spectrometry 

ISO International Organization for Standardization 

LG Leaded gasoline 

MTBE Methyl tertiary butyl ether 

NBR Acrylonitrile (or nitrile) butadiene rubber 

NREL National Renewable Energy Laboratory 

OBP DOE Office of Biomass Program 

Onset Eꞌ Storage modulus associated with the onset of the glass to rubber transition 

ORNL Oak Ridge National Laboratory 

PEI Petroleum Equipment Institute 

PTFE polytetrafluoroethylene 

RFS Renewable Fuel Standard 

SAE Society of Automotive Engineers 

SBR Styrene butadiene rubber 

Tg Glass-to-rubber transition temperature 

UG Unleaded gasoline 

UL Underwriters Laboratories 

UST Underground Storage Tank 

VTP DOE Vehicle Technologies Program 

XPS x-ray photoelectron spectroscopy 

xi 

FOREWORD 

It is not the purpose of the ORNL-led materials compatibility studies to define the acceptable limits of 

material performance or to rate individual materials. Rather, the purpose of this study was to measure 

critical property changes (volume, hardness, mass, etc.) for representative classes of dispenser materials

in ethanol-blended test fluids. The test results are intended to be used by material designers and users to 

identify potential issues and guide the selection and development of materials compatible for use in E15 

dispensers. 

xiii 

ACKNOWLEDGMENTS 

This report and the work described were sponsored by the Biomass, Clean Cities, and Vehicle 

Technologies Programs within the U.S. Department of Energy (DOE) Office of Energy Efficiency and 

Renewable Energy (EERE). The authors gratefully acknowledge the support and editorial guidance of 

Brian Duff, Shab Fardanesh, Joan Glickman, Steve Przesmitzki, Dennis Smith, and Kevin Stork at DOE. 

This effort originated from a collaboration of Oak Ridge National Laboratory (ORNL), the National 

Renewable Energy Laboratory (NREL), and Underwriters Laboratories (UL). Our NREL collaborators 

were Kristi Moriarty and Wendy Clark. We also respectively acknowledge our UL collaborators Tom 

Chapin, Ken Boyce, Tom Fabian, and Edwin Yang, who provided substantial input, direction, and 

research assistance. This work also benefitted from discussions and suggestions provided by participants 

from the E10+ Research and Planning Meetings sponsored by the American Petroleum Institute (API). 

We are especially grateful for the technical exchanges with Prentiss Searles and Brian Knapp, from the 

API; Andrea Barbery and Mark Barolo, of the Environmental Protection Agency Office of Underground 

Storage Tanks (EPA-UST); and Bob Renkes, of the Petroleum Equipment Institute. Dennis Boyd from 

BP also provided much useful input. We also acknowledge and appreciate the thorough review and input 

provided by Marc Goodman from New West Technologies, LLC. The authors are indebted to many 

technical experts in industry and other government agencies. While these companies and their experts 

provided valuable guidance and information as noted above, this consultation does not constitute 

endorsement by their organizations. This study also benefitted greatly from the material contributions 

from Dupont and 3M and two gracious suppliers of nitrile rubbers. Their contributions and guidance on 

material selection were crucial to facilitating the experiments and subsequent analysis of the results. 

Several ORNL staff made important contributions to this work; key support was provided by Michelle 

Kidder, Harry Meyer, Raynella Connatser, John M. Storey, Brian West, Eric Nafziger, Norberto 

Domingo, Steve Whitted, and Jeff Chambers. 

The authors also wish to thank the staff of Publishing Services at ORNL for help with preparation of the 

final manuscript. 

xv 

EXECUTIVE SUMMARY 

E.1 BACKGROUND 

The Energy Independence and Security Act (EISA) of 2007 was an omnibus energy policy law designed 

to move the United States toward greater energy security and independence. A key provision of EISA is 

the Renewable Fuel Standard (RFS) which requires the nation to use 36 billion gallons of renewable fuel 

in vehicles by 2022. Ethanol is the most widely used renewable fuel, and a significant portion of the 

36 billion gallon goal can be achieved by increasing the ethanol in gasoline to 15%. In fact in March 

2009, Growth Energy (a coalition of ethanol producers and supporters) requested a waiver from the 

Environmental Protection Agency to allow the use of 15% ethanol in gasoline. In anticipation of this 

waiver being granted, uncertainties arose as to whether additional fuel ethanol, such as E15 and E20, 

would be compatible with legacy and current materials used in standard gasoline fueling hardware. In the 

summer of 2008, the U.S. Department of Energy recognized the need to assess the impact of intermediate 

blends of ethanol on the fueling infrastructure, specifically located at the fueling station. This research 

effort was led by Oak Ridge National Laboratory and the National Renewable Energy Laboratory in 

collaboration with Underwriters Laboratories. The DOE program has been co-led and funded by the 

Office of the Biomass Program and Vehicle Technologies Program. 

The infrastructure material compatibility work has been supported through strong collaborations between 

the DOE labs and UL. NREL led the effort to select and test a limited number of new and legacy fueling 

dispenser units using 17% ethanol; the actual testing was conducted at UL under subcontract to NREL. 

ORNL led the effort to evaluate the impact of intermediate blends of ethanol on a large number of 

materials (metals, elastomers, plastics and sealants) representing those typically used in dispenser 

infrastructure. The ORNL materials studies are reported herein, but additional work is under way at 

ORNL, and additional interpretation of the combined data from ORNL, NREL, and UL is expected in the 

near future. 

E.2 EXPERIMENTAL OVERVIEW 

Material selection was based on a thorough investigation of dispenser materials by the ORNL materials 

research team. Team members contacted dispenser component and elastomer/seal manufacturers and 

received input from stakeholders including UL, the Petroleum Equipment Institute (PEI), and the API 

members. Although the research team was able to identify typical dispenser materials (especially 

elastomers) according to class, specific grades and formulations could not be precisely identified. As a 

result the material selection does not necessarily include those specific grades or formulations used in 

legacy and current standard gasoline dispensers. The broad material classes that were identified for use in 

gasoline fuel dispensers include metals, elastomers, plastics, and sealants. Testing was accomplished for 

the metals, elastomers, and sealants only. During the time this report was being written, the plastic 

specimens were undergoing compatibility exposures. Therefore, only the metal, elastomer, and sealant 

results are discussed in this report. A follow-up report discussing the plastic results will be issued upon 

completion of that portion of the study. 

In this study four test fuels based on the Fuel C composition, and aggressive ethanol were examined. 

These formulations are based on test fuels described in SAE J1681, “Gasoline, Alcohol, and Diesel Fuel 

Surrogates for Materials Testing.”1

 The fuel types studied were Fuel C, CE10a, CE17a, and CE25a. Fuel 

C is a 50-50 mixture of toluene and isooctane and is representative of highly aromatic gasoline (>40% 

aromatics by volume). The other test fuels contain an aggressive ethanol solution added to Fuel C—

hence, the CE nomenclature. The numbers that follow CE refer to the volume fraction of aggressive 

ethanol added to Fuel C, and the aggressive nature is represented by the “a” at the end. The ethanol-
xvi 

bearing fuels contain an aggressive ethanol formulation containing NaCl, dilute acetic and sulfuric acids, 

and 0.9% water. All of these contaminants are found in ethanol-gasoline fuels and represent the bounds 

allowable for fuel-grade ethanol. They are also intended to minimize the length of exposure necessary to 

rigorously evaluate materials while providing a standard method of testing fuel system materials. In order 

to reflect the conditions associated with vapor recovery, selected elastomer and metal specimens were 

placed in the gaseous region above the liquid fuel line (headspace) to prevent contact with the 

moving fluid. 

The metals and alloys that were evaluated in this study included single metal/alloy coupons of 

1020 carbon steel, 304 stainless steel, 1100 aluminum, nickel 201, cartridge brass, phosphor bronze, and 

terne-plated steel. In addition, to better reflect dissimilar metal-to-metal contacts existing in the field, 

specimens composed of steel, brass, and aluminum were coupled with lead, zinc, chromium and nickel to 

create galvanic scenarios for evaluation. Corrosion was primarily assessed by measuring the mass loss for 

each exposed coupon and observing any discoloration that may have occurred. For each metal sample, 

one or more specimens were exposed to the liquid and one was exposed to the vapor region of the test 

chambers. 

The elastomer classes that were selected for study were fluorocarbon, fluorosilicone, silicone, 

acrylonitrile butadiene rubber (also known as nitrile rubber or NBR), styrene butadiene rubber (SBR), 

polyurethane, and neoprene. The test matrix included eight types of fluorocarbons and six grades of NBR, 

while the remaining elastomer types consisted of one sample only. The elastomers placed in the liquid 

phase region were evaluated for volume, mass, and hardness changes for both wetted and dried 

conditions. Dynamic mechanic analysis (DMA) was performed on each specimen to assess elasticity over 

a wide temperature range. Three specimens were exposed to the liquid phase, while one specimen was 

exposed to the vapor-only regions. The metal and elastomer coupons were loaded into the stir chambers 

which were held at 60°C for 4 weeks while being subjected to a constant flow of 0.8 m/s. 

Pipe thread sealants were introduced into the study matrix at different times; thus, they were not exposed 

to each test fluid, nor were the samples all exposed under the same test fuels. However, a standard sealant 

representative of those used in legacy equipment for gasoline and diesel use was evaluated in Fuel C, 

CE10a, and CE25a test fuels. An ethanol-resistant sealant (developed specifically for E10 and E85 use) 

and the standard sealant combined with Teflon tape were evaluated in CE10a and CE25a. A total of three 

specimens were exposed for each sealant test case, and the sealant performance was evaluated according 

to ASTM D 6396, “Standard Test Method for Testing of Pipe Thread Sealants on Pipe Tees.”2

E.3 METAL RESULTS 

Very little corrosion of any of the metallic coupons was observed from exposure to Fuels C, CE10a, 

CE17a, or CE25a. Coupons exposed to the vapor phase above each solution exhibited slight discoloration 

in some cases (particularly the brass and bronze coupons), but no loss of mass was observed for any of the 

metals exposed in the vapor regions. 

Among the coupons immersed in the different test solutions, 1020 mild steel, 1100 aluminum, 201 nickel, 

and 304 stainless steel were found to be essentially immune to corrosion for the exposure conditions 

evaluated. This result suggests that these materials are suitable for extended service in intermediate fuel 

blends of this type. Cartridge brass, phosphor bronze, zinc-plated (galvanized) steel, and lead-plated 

(terne) steel exhibited variable degrees of discoloration and minor corrosion product film formation. The 

highest corrosion rate observed among these very slightly susceptible materials was about 30 μm/year for 

the cartridge brass immersed in CE10a, and this result is still considered to be a low rate of corrosion. No 

significant corrosion was observed for the Fuel C immersions (<0.3 μm/year), and there was no apparent 

trend associated with the corrosion rate of any materials as a function of ethanol concentration in the fuel. 
xvii 

X-ray photoelectron spectroscopy (XPS) was performed on representative coupon surfaces following 

testing (to compare with results from unexposed coupons) to assess the corrosion film thickness and 

composition as a function of ethanol content in the exposure environment. The results showed that 

corrosion film composition and thickness were not dependent on fuel ethanol concentration. An example 

surface analysis of cartridge brass exposed to CE25a indicated that copper sulfide was the predominant 

corrosion product present in the surface films, and was likely responsible for the observed discoloration. 

None of the plated coupons—Cr-, Ni-, Pb-, or Zn-plated steels, Cr-plated brass, or Ni-plated aluminum—

revealed any readily observable discoloration/change or measurable corrosion (no weight loss, no 

pit/crevice initiation). Further, none of the partially plated coupons showed accelerated corrosion due to 

galvanic coupling between the plating material and substrate. 

E.4 ELASTOMER RESULTS 

All of the elastomer specimens that were exposed to the test fuels (including Fuel C) exhibited some level 

of volume swell. Ethanol was found to further increase the volume swell and produce softening. The level 

of swell is an indication of solubility, and for most elastomers tested, the highest level of swell occurred 

with either the CE10a or CE17a (not CE25a). This result suggests that the highest level of mutual 

solubility for elastomers occurs at relatively low levels of added ethanol. After drying for 20hr at 60o

C, all 

of the samples, except the fluorocarbons, exhibited some level of shrinkage and mass loss. Interestingly, 

the fluorocarbons retained a slight increase in dry mass and volume, indicating that residual test fluids 

were trapped in the microstructure (even after dry-out). 

The dominant feature of the test results is that the compatibility properties were observed to group 

according to elastomer class. The fluoroelastomers (fluorocarbons and fluorosilicone) showed the best 

retention of baseline properties of the elastomers studied. These materials incurred the lowest decline in 

physical properties of the elastomers tested in this study. The addition of ethanol did not drastically affect 

the measured properties, and the eight fluorocarbons exhibited only modest swell (around 20%) and 

softening (wet hardness decrease) upon exposure to the test fuels. The properties for the fluorosilicone 

rubber sample were found to be close to those measured for the fluoroelastomer samples. Volume swell 

was somewhat higher than the fluorocarbon results but is still considered relatively low (~20%). 

Of all the elastomers tested, silicone rubber underwent the highest level of volume expansion (>120%) 

when exposed to the test fuels. This swell was accompanied by a 20 point drop in hardness. However, 

following dry-out, the silicone sample returned to its original condition with only a slight level of 

shrinkage and mass loss. The excessive volume swell means that silicone is susceptible to fluid 

permeation and extrusion (between sealed surfaces), depending on the sealing application. As with the 

fluoroelastomers, silicone did not suffer any structural degradation from exposure to the test fluids. 

The eight NBR samples (and polyurethane) showed a pronounced increase in volume swell and softening 

when exposed to fuels containing ethanol. Exposures to Fuel C resulted in volume expansion approaching 

20% or more. When exposed to the ethanol-blended test fluids, the NBRs swelled by more than 30%. 

Likewise, the hardness values dropped an additional 10 points when ethanol was added to the test fluid. 

When all of the samples (including Fuel C exposures) were dried, 8% to 14% of the original mass was 

lost and the accompanying shrinkage was between 10% and 18%. The dried hardness was increased 5 to 

16 points, indicating that embrittlement had occurred. NBR was one of only two elastomer types (the 

other being neoprene) that exhibited significant embrittlement in the dried state, indicating that plasticizer 

components were being removed by the test fuels. The results of the NBRs showed a high degree of 

variance, which is not surprising since different NBRs are designed for a wide variety of applications. 

NBRs showed a significant increase in the glass transition temperature (a measure of potential 
xviii 

embrittlement at low temperatures) with Fuel C exposure, but the addition of ethanol was observed to 

reduce this shift rather than extend it. 

The polyurethane results essentially matched those of the NBRs, with one notable exception: 

Polyurethane became softer (not harder) when dried from the wetted state, but only for those specimens 

exposed to ethanol. The reduction in hardness (after drying) upon exposure to ethanol indicates that the 

aggressive ethanol reacted with the polyurethane, causing permanent degradation. The poor wetted 

properties combined with the high shrinkage and mass loss indicate that polyurethane may not be an 

acceptable elastomer in many sealing applications for use with fuels containing up to 25% ethanol. 

The SBR sample experienced the highest combination of swell and softening. The volume expansion 

exceeded 90%, and the hardness dropped 50 points when wet. As a result, the sample evaluated in this 

study would not be considered compatible with many sealing applications with the test fluids. SBR is 

similar to NBR in that the properties are highly dependent on additives, processing, and copolymer 

concentrations. This flexibility of design means that there may be appropriate formulations of SBR that 

will, in fact, meet a given sealing specification. 

The neoprene sample’s decrease in wet hardness was relatively low and was comparable to the 

fluorocarbon results; however, the volume swell exceeded 60%, which may limit its use. Particularly 

disconcerting was the fact that neoprene exhibited the poorest dried properties of the elastomers in the 

study. Upon drying the mass and volume were reduced 15% and 20%, respectively. Neoprene also 

exhibited a high level of embrittlement as the hardness was increased by 14 points. The high mass loss 

and shrinkage, and the accompanying increase in hardness, suggest that neoprene (along with NBR) 

contained significant levels of plasticizers prior to the exposure runs. These plasticizer additives were 

removed by the test fuels, leaving the neoprene sample in a less durable condition. 

The physical properties of the vapor-exposed specimens correlated with the results obtained for the 

wetted specimens for the elastomers tested. Embrittlement was observed for the NBRs and neoprene by 

vapor phase alone. The chemistry of the head space region will have higher concentrations of ethanol and 

isooctane (relative to toluene) due to the volatility of these fuel components. It is reasonable to assume 

that this scenario will also occur in the field as well. 

E.5 SEALANT RESULTS 

The results show that the standard sealant passed the ASTM D6396 criteria in Fuel C but did not pass 

following exposure to either CE10a or CE25a. However, when standard sealant was combined with 

Teflon tape, leaking did not occur. The results also show that the ethanol-resistant sealant product passed 

when tested with both CE10a and CE25a. Hence the standard sealants may not be compatible without the 

additional sealing provided by Teflon tape. The ethanol-resistant sealant product was successful at 

preventing leakage in CE25a according to the ASTM standard. 

It is anticipated that the results of this study will be used to assist with the design and selection of 

materials to be used in future dispensers, possibly including retrofits. The upcoming experimental 

analysis of the plastic specimens will conclude this test series, and a final report summarizing these 

conclusions will be forthcoming. It is also our intention to present these results in several open forums 

during the year, and we will be collaborating with UL on assessing polymer chemistry and solubility. 
1 

1. INTRODUCTION 

1.1 ETHANOL USE AS A TRANSPORTATION FUEL 

In the United States oil dependence is driven by the transportation sector. In fact, transportation accounts 

for 69% of the total oil consumption in the United States, and the industry itself is around 90% oil 

dependent (and the remainder being natural gas, propane, electric and ethanol).3 In 2008 the average daily 

consumption of the U.S. transportation sector was approximately 14 million barrels. This rate is projected 

to increase to around 16 million barrels per day by 2025.4

 Currently, the bulk of our oil usage is provided 

by other countries as foreign oil imports and makes up around 57% of the total oil usage.5 This 

dependency impacts our nation’s security, since our oil supply is determined partly by other countries, 

some of whom are not friendly to the United States. Foreign disruption has been shown to negatively 

impact the nation’s economy and makes the United States more vulnerable during times of international 

crisis. 

The Energy Independence and Security Act of 2007 is an omnibus energy policy law created for the 

purpose of moving the United States toward greater energy security and independence. A key provision 

of EISA is the renewable fuel standard which requires the nation to use 36 billion gallons of renewable 

fuels in vehicles by 2022. This mandate is structured to incrementally increase from 9 billion gallons in 

2008 to 15 billion gallons in 2012 and, eventually 36 billion gallons in 2022. 6 The vast majority of this 

requirement has been met using ethanol derived from corn, but other ethanol feedstocks (especially 

cellulosic-based sources) are being looked at as a means of increasing total ethanol production toward 

achieving the 36 billion gallon requirement. 6 

However, the amount of ethanol that may be blended and sold as an additive to gasoline is restricted to 

10% by volume (E10) by the EPA. 7 A small amount is sold as E85 (gasoline containing 85% by volume 

of ethanol) for use in flex fuel vehicles (FFVs), but most (approximately 90% of dispenser product) is 

sold as E10. In 2012, the RFS will require over 15 billion gallons of renewable fuel, but the renewable 

fuel mandate will continue to increase. Assuming that most of the RFS is met using ethanol, gasoline 

blenders are likely to hit a limit in the next few years, since 10% ethanol cannot likely exceed 14 billion 

gallons per year. This “blend-wall” is the maximum possible volume of ethanol that can be achieve with 

E10. Because of this limitation, there is interest in increasing the allowable concentration of ethanol in 

gasoline to meet the RFS 2022 mandate to “intermediate-level” blends, ranging from 15 to 50% ethanol 

by volume. 8

A key concern is that as the ethanol level in gasoline is increased, the fuel becomes less compatible to the 

fueling infrastructure materials, which were originally designed for E0 use. These materials are 

considered adequate (by many) for E10, and there is no notable public record of a major leak or failure 

directly attributable to ethanol use, although accelerated corrosion has occurred in some instances. It is 

conceivable that many compatibility issues that do arise have been, and are, corrected onsite and 

unreported. However, there is some concern that higher ethanol concentrations, such as E15 or E25, may 

be incompatible with current materials used in standard gasoline fueling hardware. In the summer of 

2008, DOE initiated a study to investigate the impact of intermediate blends of ethanol on the fueling 

infrastructure, specifically the dispenser hanging hardware and associated piping to the underground 

storage tank. 

The DOE program has been co-led and funded by the Office of the Biomass Program and Vehicle 

Technologies Program with technical support from the ORNL and the NREL. The infrastructure material 

compatibility work has been supported through strong collaborations and testing at UL. NREL has been 

responsible for the selection and testing of a limited number of new and legacy fueling dispensers using 
2 

17% ethanol, with the testing being conducted at UL under subcontract to NREL. These results were 

reported separately.9

 ORNL and UL performed a postmortem analysis of rubberized cork gaskets used in 

several of these dispensers, and these results are summarized in Appendix A. A separate but corollary 

study was led by ORNL to evaluate the impact of intermediate blends of ethanol on a larger number of 

materials (elastomers, plastics, and metals) used in fuel dispensers. It was expected that many of the 

materials evaluated in the ORNL study were also used in the prototype dispensers that were tested in the 

NREL study. The ORNL results form the basis of this report, but additional research is underway at 

ORNL, and further interpretation of the combined data from ORNL, NREL, and UL is expected in the 

near future. The reader will note that the term fluid is used frequently throughout this manuscript. Here 

fluid refers to the liquid state of the test fuel. 

Under ambient conditions, pure ethanol is not generally considered corrosive toward most metallic 

materials; however, as a polar molecule, ethanol will be more susceptible to having compatibility issues 

with both metals and polymers due to (1) increased polarity relative to gasoline, (2) adsorption of water, 

and (3) a high solubility parameter relative to gasoline. The first two factors are relevant to metals and 

alloys, while the latter primarily affects polymers. A detailed study measuring the electrical conductivity 

of gasoline as a function of ethanol and water concentration was performed by Kirk.10 Kirk’s study shows 

that the conductivity of ethanol-blended gasoline increases marginally with ethanol concentrations up to 

20%. However, although the conductivity numbers are low, relatively speaking, E15 is 10 times more 

conductive than E10, as shown in Figs. 1 and 2. As the ethanol concentration increases from 20% to 50%, 

the corresponding conductivity increases by more than two orders of magnitude. As a result, metal 

corrosion becomes a significant concern for ethanol blends containing 50% or higher levels of ethanol. 

The results in Fig. 2 show that water also has a pronounced effect on conductivity. As the level of ethanol 

increases, the amount of water that can be dissolved also increases. In fact, the water solubility limit 

increases the conductivity by an order of magnitude when going from E10 to E15. In addition, water itself 

is a solvent for NaCl and acids, which can lead to even higher rates of corrosion. 

Ethanol also affects the material-fluid mutual solubility associated with the fuel blend, which is an 

important parameter for gauging the compatibility of fuels with polymers. The influence of the solubility 

Fig. 1. Influence of conductivity with ethanol concentration of 

gasoline (reprinted with permission). Source: D. W. Kirk, Fuel 62, 

1512–1513 (December 1983). 

0.00E+00

5.00E-06

1.00E-05

1.50E-05

2.00E-05

2.50E-05

3.00E-05

3.50E-05

0 10 20 30 40 50 60

Conductivity, 1/

Ω-m

Ethanol concentration, vol%
3 

Fig. 2. Influence of conductivity as a function of ethanol and 

water content (reprinted with permission). Source: D. W. Kirk, Fuel 

62, 1512–1513 (December 1983). 

parameter is complex; however, solvents and solutes having similar solubility parameters will have a 

greater affinity for permeation and dissolution.11 A simplified representation of solubility as a function of 

ethanol concentration in gasoline is shown in Fig. 3. The shaded zone in the chart represents the range of 

solubility parameters for many dispenser polymers. As the ethanol concentration increases from zero to 

15%, it effectively raises the solubility parameter (measured as the total Hansen Solubility Parameter) so 

that it approaches the values of most dispenser polymers. Therefore, the propensity for the fuel to 

permeate into and dissolve polymeric components is enhanced. It is important to note that, in reality, 

solubility is determined from multiple thermodynamic factors, and that the highest level of mutual 

solubility for a given polymer does not necessarily match precisely with the theoretically-derived 

parameters which have been simplified in Fig. 3. Standard gasoline fuel delivery systems contain 

elastomeric materials having excellent compatibility and stability with hydrocarbon fuels. However, the 

ethanol molecule is relatively small and highly polar due to the –OH group. In addition, the tendency to 

introduce hydrogen bonding is high. These features enable its permeation into and interaction with the 

elastomer structure, which can result in swelling and softening of elastomers. Another negative feature 

associated with permeation is that soluble components, especially plasticizers added to impart flexibility 

and durability in the elastomer, may be leached out, thereby affecting the mechanical properties of the 

compounded elastomer component and degrading the ability of the component to perform its intended 

function. This affect is exacerbated under alternating wet/dry conditions. 
4 

Fig. 3. Total Hansen Solubility Parameter as a function of ethanol concentration. 

The blue horizontal band represents the solubility range of many dispenser polymers. 

Several studies have been undertaken to evaluate the compatibility of ethanol with engine materials, 

especially those used in fuel system components such as pumps, and much of this work has recently 

focused on the intermediate E15, E20, and E25 blends.12–18 However, little work has been reported on the 

compatibility of these fuels to standard fuel dispenser materials, including sealants. Additionally the 

ethanol compatibility of high-performance fluoroelastomers needs to be evaluated since these materials 

are considered potential alternatives to the current rubber materials used dispenser seals and o-rings. 

Elastomers are a class of polymers used predominantly in most sealing applications. They are widely used 

in fuel dispenser systems and exist predominantly as o-rings and gasket-type seals. Modern elastomeric 

sealing compounds typically contain 50% to 60% base polymer and are often known as rubbers; the 

balance consists of various fillers, vulcanizing agents, accelerators, aging retardants, plasticizers, and 

other additives used to engineer physical properties to meet specific sealing requirements.19-20 Synthetic 

rubbers are grouped according to their chemical structure, and several elastomers commonly used in fuel 

dispensers are listed in Table 1. 

It is important to note that cork gaskets frequently used in petroleum sealing applications are typically 

impregnated with one of these rubber types and are commonly known as rubberized cork. The resulting 

performance is determined by both the properties of the rubber and cork components. In this study we 

evaluated the performance of cork impregnated with NBR. These specimens were placed alongside the 

plastics, and therefore, these results are not reported in this report. 

10

15

20

25

30

0 20 40 60 80 100

Solubility parameter, MPa1/2

Ethanol concentration, vol.%

Range of most dispenser polymers
5 

Table 1. Rubber types used in this studya

Chemical name ASTM D1418 

abbreviation 

M-Group (saturated carbon molecules in the main macromolecule group) 

Fluorocarbon rubber FKM 

R-Group (unsaturated hydrogen carbon chain) 

Neoprene rubber 

Nitrile butadiene rubber 

Styrene butadiene rubber 

CR 

NBR 

SBR 

Q-Group (silicone in the main chain) 

Silicone rubber 

Fluorosilicone rubber 

PVMQ 

FVMQ 

U-Group (carbon, oxygen, and nitrogen in the main chain) 

Polyurethane AU a

Classifications obtained from Parker O-Ring Handbook, ORD 5700, Parker Hannifin Corp., Cleveland, Ohio. 

2. LITERATURE REVIEW OF ELASTOMER COMPATIBILITY 

WITH ETHANOL-BLENDED GASOLINE 

An extensive literature survey was performed which focused on the compatibility of elastomers and 

metals with ethanol-blended gasoline or standard test fuels. Most of the citations discussed in this report 

were provided by UL and several additional key articles were found in the trade journal Sealing 

Technology. Concerns regarding the compatibility of oxygenated gasoline with elastomers surfaced in the 

early 1980s in response to the introduction of gasohol (gasoline blended with 5 to 20% ethanol by 

volume) and methyl tertiary butyl ether (MTBE).21 The o-ring and sealing manufacturers and suppliers 

were among the first to recognize that gasoline containing either MTBE or ethanol at levels between 10% 

and 25% may increase solubility with existing elastomer seals, leading to potential loss of durability. 

Unfortunately there has not been much research on elastomer compatibility with ethanol-blended 

gasoline. In fact, methanol-based compatibility studies were much more prevalent in the open literature 

than ethanol-based efforts. Also, the range of elastomers studied in the literature has also been quite 

limited. The majority of the work has focused on fluorocarbons and NBRs rather than other elastomer 

types. 

The key properties used to assess seal performance in a test fluid are wet volume swell, hardness, and 

shrinkage during drying. Swell is usually accompanied by a decrease in hardness (softening), which also 

affects performance. Most o-ring manufacturers and suppliers use a common rating system to assess fluid 

compatibility.20, 22–24 A sample rating system is shown in Table 2 and is based on a combination of 

published literature, laboratory tests, field experience, and informed judgments. It is important to note that 

this system is based on volume swell alone, which is only one indicator of elastomer–fluid compatibility. 

O-ring suppliers are careful to mention, however, that the above rating system does not indicate accuracy 

or suitability for all applications. In fact, the Dichtomatik O-Ring Handbook22 clearly states that users of 

Table 2. Standard compatibility rating system 

Rating Description Volume change, % 

1 Little or no effect <10 

2 Possible loss of physical properties 10‒20 

3 Noticeable change 20‒40 

4 Excessive change >40
6 

their products must conduct their own evaluations to determine suitability. The particular application will 

dictate material specifications. For instance, for static o-ring applications (where the o-ring is not 

compressed against a moving surface), volume swells up to 30% (and sometimes 50%) can usually be 

tolerated. In contrast, for dynamic applications involving rotational or directional surface movement (such 

as those used in valves), the acceptable swell limit is often less than 20%. These limitations are 

considered general rules, and exceptions to these rules exist depending on the application. Shrinkage 

caused by dry-out is also a prime cause of failure. For most o-ring applications, the maximum allowable 

shrinkage is around 3‒4% of the original volume for either static or dynamic applications. Hardness 

change is another critical property that needs to be measured. Excessive softening will lead to extrusion 

and extraction, which can result in a loss of mechanical integrity (such as compressibility, compliance and 

tensile and impact strength), while hardening may cause embrittlement and cracking. 

O-ring and sealant manufacturers have internal research programs to evaluate material–fuel compatibility, 

and manufacturers such as Parker, Precision Polymer Engineering, O-rings Incorporated, and Dichtomatik 

all provide compatibility charts to assist with polymer selection for use with a particular solvent.20, 22–24

Rankings are based primarily on pure solvents (not blends), but they do typically include a relative 

comparison of their products with ethanol and pure gasoline components such as isooctane and toluene 

with their products. The recommendations listed in the manufacturer’s charts are based on experimental 

data, and the rankings are based on comparisons with similar materials. These charts are intended to serve 

as general guidelines only. 

Important properties for assessing seal performance include primary properties such as volume change 

(swell and shrinkage), storage modulus, hardness, and the low-temperature operating limit. Since 

hardness is related to the modulus, it is often reported instead of the modulus. Other important properties 

that are less frequently reported are tear and abrasion resistance. The storage modulus is often considered 

to be the best indicator of toughness and is one of the key parameters for predicting seal performance. The 

storage modulus and lower temperature limit are both determined using DMA measurement, while the 

volume change is determined from the change in measured volume. Because of the cost and time 

necessary for DMA measurement, volume change and hardness are the two most frequently employed 

methods for assessing elastomer performance. 

In 1999, Paul Westbrook of Shell Oil Company published a technical assessment of literature pertaining to 

the compatibility and permeability of oxygenated fuels to materials in underground storage and dispensing 

equipment.21 Westbrook’s review covered studies that were published from 1975 to 1997. Although the 

survey focused on MTBE added to gasoline, his team was also able to gather information pertaining to 

ethanol-blended gasoline as well. Table 3 shows the key properties that pertain to compatibility for 

isooctane, toluene, and ethanol. 

Because the focus of this study was on intermediate levels of ethanol (10‒25 vol %) and relevant 

dispenser materials, this review was limited to ethanol and gasoline blends and elastomers used in fuel 

dispenser components. Dispenser components are herein defined as those systems pertaining to fuel 

handing from the fuel truck to the underground storage tank (UST) and from the UST to the dispenser. 

Vapor recovery systems are included, but the UST is not. Several studies dealt with vehicle fuel system 

Table 3. Key properties of isooctane, toluene, and ethanol associated with fluid-elastomer compatibility 

Chemical Formula Mole wt. Vapor pressure at 

38°C (psi) 

Density 

[at 20°C (g/cc)]

Boiling point 

(°C) 

ΔHvap

(BTU/lb) 

Isooctane C8CH18 114.2 1.7 0.6919 99.2 271 

Toluene C7H8 92.1 1.0 0.8660 110.6 363 

Ethanol C2H6O 46.0 2.3 0.7890 78.3 920 
7 

component evaluations and, as a result, do not provide information pertaining to volume swell and 

hardness. These studies usually report a pass/fail result for the component tested. 

Studies providing swell and/or hardness data are summarized in Table 4 along with the test fluids and 

elastomers studied. The majority of the reported efforts were directed towards fluorocarbons and NBRs. 

This emphasis is not surprising since fluorocarbons are known to have excellent fuel resistance and NBR 

is the most common elastomer used in seals and those applications. However, as shown in the table, 

several studies did include fluorosilicone and polyurethane, and one included neoprene. The other feature 

that stands out in the table is that the test fuels are either based on gasoline or Fuel C. Fuel C is a Society 

of Automotive Engineers (SAE) standard test fuel composed of a 50/50 volume blend of toluene and 

isooctane.1

 All of the studies listed in Table 4 provide results for swelling, and some include other 

Table 4. Test fuel and elastomer type listing for key references 

Reference Test fuel(s) Elastomer type

P. Touchet, B. Zanadis, M. Fischer, and P. E. Gatza, Materials 

Compatibility Studies with Fuel/Alcohol Mixtures, Technical Report 

2366, U.S. Army Mobility Equipment Research and Development 

Command, Fort Belvoir, VA, July 1982 

Fuel C 

Unleaded gasoline 

(UG) 

Leaded gasoline 

(LG) 

UG10 

LG10 

UG20 

LG20 

Fluorosilicone 

Fluorocarbon 

NBR 

Polyurethane 

R. F. Karg, C. L. Hill, K. Dosch, and B. Johnson, “Ultra-high CAN 

Polymer In Fuel System Application,” SAE 900196 

Fuel C NBR 

I. A. Abu-Isa, “Effects of Mixtures of Gasoline with Methanol and with 

Ethanol on Automotive Elastomers,” SAE Paper No. 800786 

Indolene 

E10 

E15 

E20 

E25 

E50 

E75 

Fluorosilicone 

Fluorocarbon 

NBR 

Polyurethane 

G. Micallef and A Weimann, “Elastomer Selection for Bio-fuel 

Requires a Systems Approach,” Sealing Technology, January 2009 

CE22 

CE85 

Fluorocarbon 

A. Ertekin and N. Sridhar, “Performance of Elastomeric Materials in 

Gasoline-Ethanol Blends-A Review,” Paper no. 09533, CORROSION 

2009 Annual Conference and Exhibition, NACE International, Atlanta 

R. D. Stephens, “Fuel and Permeation Resistance of Fluoroelastomers 

to Ethanol Blends,” ACS Technical Meeting of the Rubber Division, 

Cincinnati, OH, October 2006 

Fuel C 

CE10 

CE20 

CE50 

CE85 

E100 

Fluorocarbon 

A. Nersasian, “The Use of Toluene/Isooctane/Alcohol Blends to 

Simulate the Swelling Behavior of Rubbers in Gasoline/Alcohol Fuels,” 

SAE Paper No. 800790 

Gasoline 

Isooctane/toluene/ 

ethanol blends 

Fluorocarbon 

Fluorosilicone 

NBR 

L. Nihalani, R. D. A. Paulmer, and Y. P. Rao, “Compatibility of 

Elastomeric Materials with Gasohol,” SAE Paper No. 2004-28-0062 

Gasoline 

E10 

E20 

Fluorocarbon 

NBR 

B. Jones, G. Mead, P. Steevens, and C. Connors, The Effects of E20 on 

Elastomers used in Automotive Fuel System Components, Minnesota 

Center for Automotive Research, Minnesota State University, Mankato, 

February 22, 2008 

Fuel C 

CE10a 

CE20a 

Fluorocarbon 

NBR 

Neoprene 
8 

measurements such as hardness and tensile properties. We were unable to find relevant DMA data on 

polymers exposed to ethanol–gasoline fuel blends in the literature. As a result, there are no comparisons 

on the effect of ethanol on the lower temperature limit or the storage modulus relationship to temperature, 

which is, of course, important in an actual sealing application. 

The most comprehensive study we found was performed by Touchet et al.25 on evaluating the corrosion 

and degradation of various elastomers, plastics, and metals in a variety of test fuels. The elastomer types 

included in this investigation were fluorocarbons, fluorosilicone, polyurethane, and NBRs. The test fuels 

included Fuel C, unleaded (32.8% aromatics) and leaded gasoline (aromatic content of 29.7%), E10, and 

E20. This study is the only one so far identified that provided a direct comparison of elastomer 

performance of Fuel C with pump-grade gasoline; in this case the pump fuels were unleaded gas (UG) 

and leaded gasoline (LG). Selected elastomer results for volume swell and hardness are shown in Figs. 4 

and 5, respectively. 

As expected, the fluorocarbons showed the best fuel and ethanol resistance. The fluorosilicone exhibited 

20% volume swell, which is consistent with other studies, but the level of softening was much higher than 

the NBRs. The results for the NBRs and polyurethanes were mixed and depended on the grade for each 

material. These results were consistent with other studies showing that low acrylonitrile (ACN) content 

leads to higher swell and loss of hardness.13 The Touchet et al. study was one of the few to include 

polyurethane, and the results show that the polyurethane samples were highly susceptible to degradation 

for gasoline containing 10 and 20% ethanol by volume. 

Another important aspect of this study was the comparison of the base fuels (Fuel C, UG, and LG) for 

each material type. For each elastomer tested, UG produced a small, but significantly higher level of swell 

than LG. For fluorosilicone, both fluorocarbons, low nitrile NBR, and one polyurethane material, Fuel C 

caused much higher levels of swell and softening than the pump-grade gasolines. The higher aromatic 

content of Fuel C (50% aromatic toluene) compared to the LG (29.7% aromatic) and UG (32.8% 

aromatic) is likely responsible for this effect. Nersasian26 also examined at the swelling behavior of 

fluorocarbon, fluorosilicone, and NBR in fluids composed of toluene and isooctane. For each material, the 

volume swell increased with toluene (or aromatic) content. 

Fig. 4. Volume swell results for selected elastomers for 

different test fuels. Data obtained from Touchet et al., Materials 

Compatibility Studies with Fuel/Alcohol Mixtures, Technical Report 

2366, U.S. Army Mobility Equipment Research and Development 

Command, Fort Belvoir, VA, July 1982.

0

10

20

30

40

50

60

70

80

90

Percent Volume Swell

Fuel C

LG

UG

LG10

UG10

LG20

UG20
9 

Fig. 5. Decline in hardness for selected elastomers for 

different test fuels. Data obtained from Touchet et al., Materials 

Compatibility Studies with Fuel/Alcohol Mixtures, Technical Report 

2366, U.S. Army Mobility Equipment Research and Development 

Command, Fort Belvoir, VA, July 1982. 

A study by I. Abu-Isa27 considered the effects of ethanol-blended gasoline on fluorocarbon, fluorosilicone, 

NBR, and polyurethane. The measured properties were tensile strength, hardness, and volume change on 

wetted specimens. The elastomer samples were exposed to the test fuels containing 0, 10, 15, 20, 25, 50, 

and 75% ethanol by volume at room temperature for 72 hr. A federal certification gasoline known as 

indolene was the base fuel. In this study, the fluoroelastomeric materials (fluorocarbon and fluorosilicone) 

were the most fuel resistant. E15 produced the highest swell for the fluoroelastomers, which was 7% and 

20% for fluorocarbon and fluorosilicone, respectively. These results are consistent with those obtained from 

Touchet et al.25 for these materials. Polyurethane and NBR reached a maximum swelling of 56% and 99%, 

respectively. For polyurethane the highest volume expansion occurred for E20, while NBR had its highest 

value for E25. Interestingly, neoprene exhibited a maximum swell of 96% for the E0 exposure. The two 

fluoroelastomers, polyurethane and NBR, exhibited their highest swelling at relatively low blends of ethanol 

(15‒25%). As a result, intermediate levels of ethanol added to gasoline are of greatest concern for 

degradation of these materials. Neoprene, on the other hand, was most affected by the gasoline, and swelling 

actually decreased with the addition of ethanol. 

Micallef et al.28 also examined the volume change (and hardness) of fluorocarbons. In contrast to 

I. Abu-Isa24 and Touchet et al. (21), Micallef used Fuel C as the control and base fluid for the ethanol 

blends. The two fuel chemistries were CE22 and CE85. His results showed that CE22 increased the 

volume by 32%, while the CE85 test fuel had a much smaller effect (16%). Once again the lower level of 

ethanol was found to be more soluble than high ethanol concentrations. The wet hardness was also 

observed to drop 14 and 18 points for exposures to CE22 and CE85, respectively. Normally hardness 

correlates with degree of swell. However, this result may indicate that although CE85 did not permeate to 

the level of CE22, the increased presence of oxygen (and probably water, salts, and acids) associated with 

the higher ethanol was able to react with and affect the surface properties of the fluorocarbons. More 

research on the effects of high levels of ethanol on fluorocarbons is needed to better understand the 

reaction chemistry that is taking place on the surface of the fluorocarbons. The level of swell observed in 

the fluorocarbons (in this study) was greater than the values obtained by Abu-Isa. This result is expected 

since Fuel C has a much higher aromatic content than the indolene-based experiments performed by Abu0

5

10

15

20

25

30

Point Decrease in Hardness

Fuel C

LG

UG

LG10

UG10

LG20

UG20
10 

Isa. Unfortunately, Micallef et al. did not report the swell associated with Fuel C exposure, and therefore 

was unable to assess the Fuel C contribution to the overall swell. 

Another study which used Fuel C as the base test fluid was performed by R. Stephens29 and summarized 

by A. Ertekin and N. Sridhar.30 Stephens exposed six different Viton fluorocarbons to Fuel C, CE10, 

CE25, CE50, CE85, and ethanol for 672 hr at 40°C. Measureable swell was obtained from exposures to 

Fuel C and varied from 6%‒12%, depending on the fluorocarbon type. The addition of ethanol further 

increased the swelling. The highest level of swell was reported for exposure to CE25, which varied from 

12–26% depending on the fluorocarbon type. In general swelling was observed to decrease as the fluorine 

content of the elastomer increased. 

A study by Jones et al.13 was performed to determine whether E20 had a greater impact than E10 on the 

volume and mass change for fluorocarbon, NBR, and neoprene. This study differed from the other 

investigations in that it used the aggressive ethanol formulation described in SAE J1681. As a result, the 

test fuels contained a small amount of water containing trace levels of acetic and sulfuric acids and 

sodium chloride. All of these contaminants are found in dispenser-grade ethanol. Fuel C was used as the 

control. Another key difference from the other studies was that each sample was immersed in the test 

fluid for 500 hr at 55°C. In contrast, many of the other studies (mentioned in this review) exposed the 

specimens to the test fluids for approximately 70 hr at room temperature conditions, and for different 

exposure times. As a result of the more aggressive test conditions, the levels of swelling were higher than 

the values obtained from other studies. The wetted and dried volume changes for each elastomer are 

plotted in Fig. 6. The fluorocarbon swelled around 30% upon exposure to Fuel C and CE10a, while 

CE20a increased the volume by more than 40%. When dried, the fluorocarbon specimens maintained a 

slight volume increase, indicating that a low level of residual fuel remained in the polymer structure. This 

conclusion is supported by the mass measurements, which showed a corresponding increase in the dry 

mass. The two NBR samples provided mixed results: the medium-ACN NBR exhibited much higher 

Fig. 6. Percent change in volume for selected elastomers exposed to 

Fuel C, CE10a, and CE20. Data obtained from B. Jones et al., The Effect of 

E20 on Elastomers Used in Automotive Fuel System Components, Minnesota 

Center for Automotive Research, Minnesota State University, Mankato, 

February 22, 2008. 

-20

0

20

40

60

80

100

120

Percent Change in Volume

Fuel C

CE10a

CE20a
11 

swell but shrank less than the high-ACN NBR after drying. In fact the high-ACN NBR produced the 

lowest level of swell among the elastomers studied. This observation is noteworthy since fluorocarbons 

exhibited the lowest level of swell in the other studies. Both NBR samples and neoprene exhibited 

shrinkage after drying, and the mass loss correlated with the amount of shrinkage observed. This result 

indicates that material was being extracted from NBR and neoprene by the test fluids. If the extracted 

material is a plasticizer additive, then the dried specimens would exhibit embrittlement and a loss of 

durability. In contrast to the other rubbers, neoprene exhibited a decrease in swell with ethanol content. 

However the resulting shrinkage (during dry-out) was more significant for the samples exposed to CE10a 

and CE20a. 

It is important to note that the volume swell for the fluorocarbon specimens exposed to Fuel C in the 

Jones study was about 30%, a much higher value than the results shown in the Touchet and Stephens 

studies. Touchet reported a 20% swell for exposure to Fuel C, while Stephens reported a range of 

6%‒12%. This discrepancy may be due to compositional difference between the fluorocarbons tested, or 

due to the higher temperature, which would enable the fluid to more completely permeate the 

fluorocarbon structure, thereby producing more swell. Unlike the fluorocarbons, NBR has a much higher 

porosity, and therefore, permeation of fluid would be less sensitive to duration and temperature. 

The literature survey shows that maximum volume swell for most elastomers occurs for ethanol 

concentrations between 10% and 25%. In addition, the volume and hardness can vary considerably 

according to elastomer type. Within each elastomer class, the swell and hardness change are subject to 

variability as well. This was especially true for NBRs, which have a wider variability in formulation and 

processing than most other elastomer types. Low- and medium-ACN NBRs exhibited very high volume 

swelling compared to NBRs of high ACN content. However, the addition of ethanol was also shown to 

significantly increase the volume swell of all NBR specimens. 

Although the fluorocarbons typically exhibited less swell and a smaller drop in hardness than the other 

elastomers studied, they were affected by ethanol, which increased swell and softening. Within each study 

the fluorocarbon samples typically showed the least amount of variability in volume swell and hardness. 

However, upon drying the fluorocarbons did not shrink or lose mass. Only one study evaluated 

fluorosilicone rubber, and the degree of swell increased only slightly with increased ethanol content. The 

fluorosilicone exhibited a relatively low volume swell of around 20% for the fluids that were studied; 

however, the level of softening was significant. Polyurethane was found to be highly susceptible to swell 

by ethanol, although the results showed considerable variability between the two samples tested. The only 

rubber to have reduced swell when exposed to fuel containing ethanol was neoprene. Neoprene swelled 

110% from exposure to Fuel C compared to 80% for exposure to CE20. Unfortunately, both of these 

values would be considered excessive for most sealing applications. 

In summary, a review of pertinent studies has shown that most elastomers exhibit some level of swell 

upon exposure to gasoline. The addition of ethanol to gasoline will increase the swell of most elastomers 

(except neoprene), and maximum swell occurs at ethanol concentrations between 10% and 25%. 

Accompanying the volume increase is a corresponding drop in the hardness, and the combination of high 

swell and increased softening would reduce the effectiveness of the seal. For the test fuels used, the 

aromatic content also tends to increase elastomer swelling. Therefore, aromatic content of the fuel needs 

to be considered when designing seals. Fluorocarbon and NBR were the most studied elastomer types, 

and fluorocarbon performance was observed to improve with increasing the fluorine concentration, while 

NBR performance improved with increasing ACN concentration. However, many factors, such as 

processing, additives, and polymer quality, affect fuel compatibility. As a result it is impossible to state, 

without field experimentation, which elastomer is best suited for a given application. Interpretation is also 

complicated by the fact that each investigator used different test conditions and test fluids. Thus it is 

difficult, if not impossible, to compare results from the different studies. This lack of experimental 
12 

standardization between researchers, combined with the limited amount of data available, was a primary 

motivation for the comprehensive ORNL-led study presented in this report. 

2.1 REVIEW OF DOE ETHANOL MATERIAL COMPATIBILITY STUDIES 

The DOE Office of the Biomass Program (OBP) and the Office of Vehicles Technologies Program 

(OVT) have funded multiple studies at different locations examining the impact of ethanol on dispenser 

and vehicle materials. These studies are similar in scope and complementary. The first study conducted 

by ORNL evaluated the performance of prototype fuel dispenser components in two recirculating 

(dynamic) test fluids, one representing E85 and the other E25. This study examined and characterized the 

changes in fuel chemistry with time of exposure. The other two follow-on studies at ORNL were directed 

towards assessing material performance with exposure to test fluids. These materials studies necessitated 

the construction of large stir chambers to enable multiple coupon exposures under tightly controlled 

conditions of temperature, pressure, and fluid flow rate. The ORNL-led materials studies were performed 

in conjunction with an effort by UL and NREL to evaluate new and used full-scale dispensers with 

CE17a. In the UL/NREL study, fuel samples were taken periodically from one new and one used 

dispenser and analyzed to determine if contaminants can be traced to the dispenser polymer materials 

exposed to the test fluids. In addition, NREL in collaboration with the Coordinating Research Council 

(CRC) is evaluating the impact of increased ethanol concentration on vehicle fuel system components.18 

2.1.1 ORNL Dispenser Study Using CE25a and CE85a 

In 2007, ORNL began a study (in collaboration with NREL and UL) to evaluate the compatibility of fullscale dispenser hardware with recirculating test fluids. The E85 dispensers in use at that time were not 

UL-listed, prompting UL and DOE to initiate a study assessing dispenser hardware compatibility with 

E85. However, the UL tests were limited to static fluid experiments, and concerns were voiced that the 

static environment may overlook features (such as erosion and passive film removal) that may actually 

exist as a result of moving fluid. As a result, the DOE Clean Cities Program supported ORNL in setting 

up a dynamic-based study, which was more reflective of actual field conditions. 

The test fuels studied were CE25a and CE85a. Both of these fuel formulations are standard SAE J1681 

aggressive mixtures developed for accelerated compatibility testing with ethanol-blended gasoline. In 

each case the gasoline portion was Fuel C (a 50/50 mix of isooctane and toluene), while the ethanol 

portion contained up to 0.9% water plus trace levels of NaCl and acetic and sulfuric acids (aggressive 

ethanol). 

ORNL received two prototype fuel dispensers from UL including two air-driven diaphragm pumps. The 

dispenser components were set up for dynamic operation in which the test fluids were recirculated during 

operation. The CE25a and CE85a dispensers recirculated the fluids at a rate of 6.3 and 7.9gal/min, 

respectively. (The source of flow rate difference between the two units was not determined but was likely 

due to differences in fuel viscosity.) The dispensers were run for 7–10 hr of continuous operation Monday 

through Friday for 15 weeks during the heat of the summer in 2008. During the summer test period, the 

temperature ranged from 10 to 40o

C. Fluid samples were taken periodically to characterize and measure 

the level of contaminants (metals and especially hydrocarbons) present in the fluid in order to identify 

components and materials at risk to degradation. At the conclusion of the 15 week period, the fluids were 

replaced and run for a second 15 week period during the winter months. Further experimental details are 

provided in Appendix B. 
13 

2.1.2 ORNL CE20a Compatibility Study of Fluorocarbons and Metals 

The full-scale dispenser study was followed by a controlled exposure study to investigate the 

compatibility of selected metals and elastomers with an aggressive E20 formulation. The purpose of the 

study was to confirm the utility of a specially-designed and sealed chamber to evaluate the compatibility 

of fluorocarbons, one NBR sample, and selected metals and alloys with a CE20a test fluid. These 

materials were evaluated as individual coupons and not as part of a component (such as a valve). The 

metals selected for the experiment covered those used in standard fuel dispenser hardware and included 

several grades of carbon and stainless steel, brass, bronze, and copper. A report detailing the test protocol 

and metal analysis was published in 2010 by Pawel et al. at the conclusion of this effort.31 The elastomers 

that were investigated included eight fluorocarbon types provided by DuPont and 3M. The metals were 

evaluated for mass loss and surface analysis, while the elastomeric materials were evaluated for tensile 

properties, hardness, and swelling. The specimens were placed inside specially designed chambers known 

as stir tanks or stir chambers (Fig. 7) that allowed multiple (and simultaneous) specimen exposures to a 

fluid flow of 0.8 m/s while maintaining a constant elevated temperature of 60°C. The combination of 

dynamic flow coupled with elevated temperature and aggressive fuel chemistry offers the potential to get 

meaningful comparative results in a relatively short time frame. The results of this study showed that 

meaningful results (for elastomers and metals) could be obtained for a 4-week exposure period. The 

study confirmed the stir chamber approach to screen large numbers of samples rapidly in order to assess 

compatibility of fuel dispenser materials and guide the identification and incorporation of ethanolresistant materials. Further experimental details are provided in Appendix C. 

Fig. 7. Experimental stir chamber. 
14 

3. ORNL FUEL DISPENSER INFRASTRUCTURE MATERIALS STUDY: 

METALS, ELASTOMERS, AND SEALANTS 

The fluorocarbon and metal coupon study confirmed the operational performance and utility of 

experimental stir chambers to evaluate large numbers of coupons efficiently. However, the polymers 

selected for the previous study were limited to eight fluorocarbons and one NBR rubber and did not 

include many of the polymers typically used in actual dispensers. As a result, ORNL decided to perform a 

coupon-based screening study to include every material type used in fuel infrastructure system 

components. These materials included those that are in contact with the fuel from the delivery truck to the 

UST (Fig. 8) and from the UST to the hanging hardware (Fig. 9). The purpose was to assess the 

compatibility of representative infrastructure materials with E15 and up to E25 and to assess the rate of 

change of material properties at these concentrations of ethanol. Sealants were also added to the test 

matrix since anecdotal evidence suggests that pipe joints present a leak risk. One other limitation noted 

from the previous study was that the metal specimens did not accurately reflect actual field conditions; 

that is, metal components are frequently joined or in contact with dissimilar metals. As a result, the 

follow-on comprehensive study included metal and alloys partially coated with either nickel or chromium 

to create a galvanic couple to better reflect field conditions. 

This study began in 2009. The dynamic stir chambers were used to evaluate the compatibility of the 

elastomer and metal coupons and sealants. The fuel types that were used in the evaluation were Fuels C, 

CE10a, CE17a, and CE25a. The specimens were exposed for 4 week periods and then subsequently 

analyzed for changes in appearance, volume, mass, and hardness. DMA was also used to assess sealing 

characteristics. 

It is important to note that unless a specific material coupon disintegrated or suffered obvious visible 

damage, it could not stated with certainty how it would perform in the field. Therefore, the purpose of this 

study was not to set failure criteria associated with material compatibility but rather to screen a large 

Fig.8. Schematic showing dispenser materials and components from the delivery truck to the UST. 

Caps

(polyurethane, SS, nitrile rubber)

Jack Screw

(see adapter)

Spill container

(Al, fluorosilicone, nylon)

Adapter (Bronze, Al, polyurethane,

Nylon, SS, nitrile rubber)

Tank Bottom

Protector (Al, SS)

Overfill protection

valve (see adapter)

Pressure Vacuum Vent

(polypropylene, SS, Al)

Liquid

Vapor

Extractor fitting (polyurethane,

iron, Zn alloy)

Ball float vent valve

(steel, SS)
15 

Fig. 9. Schematic showing dispenser materials and components from the UST to the nozzle. 

sampling of materials typically used in the infrastructure showing the effect of ethanol concentration on 

relevant material properties, such as volume swell and hardness. The resulting data will be available to 

dispenser designers and manufacturers, and it is they who will determine whether the material 

performance is acceptable or not. The intent of the material selection was to match, to the extent possible, 

those found in full-scale dispensers and related equipment. The limited availability of this information, 

however, has created some lack of precision as to which specific formulations to test. 

3.1 MATERIALS AND SPECIMEN PREPARATION 

The materials examined in this study reflect many of the components used in fuel dispenser components, 

as shown in Figs. 8 and 9. Guidance on the selection of specific materials (especially polymers) was 

provided by UL, the API, individual oil companies, and material suppliers. Much information on material 

selection was provided by the OPW and Dresser-Wayne websites regarding dispenser hardware 

subsystems and components. Unfortunately, a comprehensive compilation of all legacy materials could 

not be made since the research team did not have access to the material history and inventory for each 

dispenser component. In spite of this limitation, a fairly representative matrix of dispenser material types 

was obtained, although the chosen materials may not be the formulations in actual use. For instance, seals 

composed of co-polymers such as NBR and SBR may have different amounts of butadiene, depending on 

the properties desired and the applications used. Additionally, there is a wide range in the type and 

amount of additives compounded within the base polymer to adjust properties and appearance. Many 

formulations are proprietary, and the actual composition of the rubber product is unknown. Testing each 

formulation for each elastomer type was not practical, therefore, testing was limited to samples 

representative of a specific elastomer class typical of those used in dispenser hardware. 

Emergency Shear Valve

Protector (Iron, steel, brass, SS, 

Teflon, polyurethane)

Liquid

Vapor

Vapor Line Shear Valve

(Iron, fluorocarbon, 

polyurethane)

Flexible connector

(SS, fluorocarbon, NBR)

Nozzle (Nylon, Al, 

fluorocarbon, Silicone rubber, 

NBR, fluorosilicone, HDPE)

Flow limiter (Al, steel)

Breakaway valve (nylon, 

HDPE, fluorocarbon, NBR, 

fluorosilicone)

Swivel (SS, fluorocarbon, 

NBR)

Ball float vent valve

(steel, SS)

Extractor fitting (iron, 

polyurethane, Zn alloy)

Pump

Piping (nylon, PVDF, PPS, 

PK) 

Hose (NBR)
16 

The results from the earlier fluorocarbon-metal coupon study showed that maximum permeability was 

achieved after 1 week of exposure to either the Fuel C or the CE20a test fuels. Likewise, the corrosion 

rate of the metal coupons did not change significantly for exposure periods of 1 week or 4 weeks. 

Although 1week appeared to be sufficient, 4 weeks was selected as the exposure period since it allowed 

for more accumulation of effects (permeation and leaching or accumulated corrosion) than a 1 week 

period would allow. 

3.1.1 Metals and Alloys 

The metals and alloys that were selected for the ORNL CE20a dispenser compatibility study were also 

used in this investigation. However, to better reflect actual field conditions, a second set of plated 

specimens had the coating partially removed to form a galvanic couple. The photograph shown in Fig. 10 

shows the appearance of two galvanic specimens: nickel-plated aluminum and chromium-plated brass. A 

complete listing of the metal specimens is shown in Table 5. Brass and aluminum were galvanically 

coupled with chromium and nickel, respectively, while 1020 carbon steel was galvanically coupled to 

both metals individually. Chromium and nickel were selected because these combinations of substrate and 

plating are used in dispensers, and therefore are representative of real possibilities.. If the electrical 

conductivity of the test fuel is sufficient, measureable corrosion (mass loss) of the test metals should 

occur. In this study, one specimen per material was evaluated for exposure to the liquid and a second 

specimen was exposed to the vapor phase. These specimens were weighed before and after exposure to 

determine the level of mass loss associated with exposure. 

Coupons of each material were 5.1 × 2.0 × 0.32 cm (2.0 × 0.75 × 0.125 in.), with the exception of 

terne-plated steel and the phosphor bronze specimens, which were only 0.16 cm (0.062 in.) thick. Each 

specimen included a central mounting hole with a diameter of 0.95 cm (0.375 in.). The total surface area 

Fig. 10. Representative pre-test appearance of plated coupons after a portion of the 

plating had been removed to expose the substrate. 
17 

Table 5. Metal and alloy specimen listing

Metals having 

unmodified coupons

Coupons having partial removal of 

plating to form a galvanic couple 

304 stainless steel Terne-plated steel 

1020 carbon steel Galvanized steel 

1100 aluminum Chromium-plated brass 

Cartridge brass Chromium-plated steel 

Phosphor bronze Nickel-plated aluminum 

Nickel 201 Nickel-plated steel 

Terne-plated steel 

Galvanized steel 

Chromium-plated brass 

Chromium-plated steel 

Nickel-plated aluminum 

Nickel-plated steel 

was about 24.5 cm2 for each of the relatively thicker coupons and about 22.2 cm2 for the relatively thinner 

coupons. The specimens were handled using lint-free gloves and tweezers. Each specimen was cleaned 

(ultrasonic treatment in acetone followed by forced air drying) and weighed prior to mounting on 

assemblies for exposure. The balance used for these experiments was capable of measuring 0.00001 g, but 

as a practical consideration for coupons of this size, reproducibility of the measurements was ±0.00005 g. 

Single specimens of each material were exposed using a stainless steel and Teflon mounting bracket 

(Fig. 11). Teflon shoulder washers were used to eliminate unwanted metal contact between the metallic 

specimens and the stainless steel mounting hardware. In addition a Teflon crevice washer was placed on 

one side of each test specimen to prevent specimen-to-specimen contact. All metallic components of the 

mounting bracket were type 304 or type 316 stainless steel. The nut and bolt arrangement was tightened 

until the stainless steel split washer (between the nut and mounting bracket) was completely flattened 

against the bracket surface. Typically, this caused a slight compression of the Teflon components. 

XPS was performed on selected coupon surfaces following testing (to compare with results from 

unexposed coupons) to assess the corrosion film thickness and composition as a function of ethanol 

content in the exposure environment. 

Fig. 11. Mounted specimens and mounting bracket. 
18 

3.1.2 Elastomers 

As shown previously in Figs. 8 and 9, many dispenser components use the same types of elastomers. Two 

classes of elastomers (fluorocarbons and NBRs) contained more than one sample type. The eight 

fluorocarbons used in this investigation are designed for different applications, and therefore differ from 

each other in fluorine content, additives, and curing process. Several of the NBR samples were developed 

for use in fuel hoses and also contain different additive packages and formulations. The other material 

classes, SBR, silicone rubber, fluorosilicone rubber, neoprene, and polyurethane, only contain one sample 

type. The following is a list of the specimens selected. 

1. Fluorocarbon rubbers: A total of eight samples were evaluated—Viton A401C, Viton B601, Viton 

GF-600S, Viton GFLT-600S, Dyneon FE5620, Dyneon FE5840, Dyneon FPO3741, and Dyneon 

LFTE6400. 

2. NBR: A total of six samples were evaluated. They are identified as NBR#1 through NBR#6. 

3. Fluorosilicone rubber 

4. Polyurethane 

5. Neoprene 

6. SBR 

7. Silicone rubber 

The elastomer specimens used the same mounting bracket as that of the metals. The specimen geometries 

were rectangular: approximately 1.27 cm wide × 3.81 cm long × 0.25 cm thick (0.5 in. × 1.5 in. × 0.1 in.). 

There were no tensile specimens used in this study. A total of three specimens were made for each sample 

and were immersed in the test fluid. In addition, one representative specimen was also placed in the 

vapor-phase region. 

Each specimen selected for fluid compatibility was pre-weighed and measured before exposure to the test 

fluid. At the conclusion of the exposure runs, the immersed specimens were quickly removed and loaded 

into a container containing enough fluid to cover the specimens and prevent drying. The wetted 

specimens were measured for volume swell and mass increase and for hardness (at five random locations 

on each specimen). The hardness protocol followed the ASTM D2240 type A scale (usually referred to as 

Shore A hardness) and was used for either wet or dry specimens.32 These specimens (along with the 

vapor-exposed samples) were then dried at 60°C for 20 hr and then remeasured (for volume and mass 

change and hardness) to assess dry cycle property changes. In addition DMA testing was performed on all 

dried fluid- and vapor-exposed specimens to determine the solvent effects on elastomer performance as a 

function of temperature. 

All DMA testing was carried out using the TA Instruments Q800 on nominal 38 mm long × 13 mm wide 

× 2 mm thick rectangular samples. The samples were placed in a single cantilever clamp having a fixed 

length of 17.2 mm and were operated in air under an oscillating amplitude of 40 microns at a fixed 

frequency of 1 Hz and a heating rate of 3°C/min. The range of temperatures over which the samples were 

evaluated varied depending on the specific elastomer that was being examined. Measurements were 

obtained using TA’s Universal Analysis software that was provided with the DMA instrument. The DMA 

instrument used in this study required that the specimens be dried prior to measurement; therefore, DMA 

measurements were not made for the wetted condition. 
19 

3.1.3 Sealants 

Pipe thread sealants were identified by ORNL with input from the oil industry and the API as critical 

materials whose compatibility with the test fuels needed to be determined. Sealant use is ubiquitous in the 

thread joint assemblies of fuel dispenser systems. Sealants are viscous materials that change state upon 

drying to become solid. The sealants most often used in gas and diesel fuel systems contain 

polytetrafluoroethylene (PTFE), better known by its trademark name Teflon. The viscous material 

containing and surrounding the PTFE particulates varies depending on the application. These sealants are 

designed to be used alone, but they are often combined with Teflon tape for additional leak protection. 

The three scenarios evaluated in this study were as follows. 

1. RectorSeal brand pipe thread sealant: This PTFE sealant is designed for use with ammonia, 

refrigerants, and heating oil. It has been widely used in legacy gasoline and diesel fuel systems to 

seal pipe threads. 

2. RectorSeal plus Teflon tape: Discussions with industry have revealed that this combination appears 

to be widely used in many applications using ethanol–gasoline fuel blends. 

3. Gasoila E-Seal: PTFE sealant developed for E10 and E85 use. 

Each sealant scenario was applied to three individual stainless steel 3/8th in. pipe plugs and evaluated 

according to ASTM D 6396 Standard Test Method for Testing of Pipe Thread Sealants on Pipe Tees. The 

plugs were screwed into a stainless steel cross to a specified torque setting of 27.1 N-m. This torque level was 

also applied to the RectorSeal/Teflon tape combination. The applied sealant and test fixture are shown in 

Fig. 12. After curing for 72 hr under ambient conditions, the open end of the cross was attached to a 

compressed air line and then submerged underwater. Approximately 100 psi of air pressure was applied to 

each test fixture, and no leaks were observed in each of the three cases. The air line was removed and the 

open end was left unplugged to allow the test fluids access to the internal as well the external surfaces of the 

test fixtures. 

Fig. 12. Thread with applied sealant and the 

test fixture with three mounted specimens. 

3.2 EXPOSURE PROTOCOL 

In order to evaluate the material performance at 60°C under dynamic operation, two chambers were 

designed to allow the coupons to be exposed at a constant flow rate and constant temperature. A 
20 

schematic representation is shown in Fig. 13. These stir tanks are equipped with a temperature control 

system to maintain a constant 60°C fluid temperature regardless of ambient conditions. Each chamber is 

capable of exposing over 300 individual specimens simultaneously. The chambers were only partially 

filled to allow a portion of the specimens to be exposed to the fuel vapors (Fig. 13). The test fuels were 

formulated following the SAE J1681protocol, and these fuels were added after specimens had been 

loaded onto the inner liner. For each chamber, the fuel was added to a level between the bottom and top 

sets of samples. The bottom sample set was completely immersed in the liquid, while the top set was left 

exposed to the vapor phase. After the specimens were loaded and the fuel was added, the lid was attached 

and the headspace was purged using compressed dry air for 5 min to ensure a consistent starting humidity 

of 0% for the vapor-exposed specimens. Next the stirring motor was turned on to provide a constant 0.8 

m/s flow of the liquid fuel and heat was applied to the tanks via the water jacket. The temperature of the 

tank fluid reached 60°C approximately 5 hr after start. The tanks were operated continuously for 28 days, 

after which the tank motor and heat were turned off and the specimens removed. The test fuel liquid level 

was set to ensure that the vapor phase specimens were not wetted by the rising fluid level at the sides 

when the paddle was operated. 

Fig. 13. Schematic representation of dynamic stir chamber. 

3.3 ANALYTICAL METHODS 

The elastomer samples were measured for mass and volume change, Shore A hardness, and DMA 

performance. These properties are commonly used to assess the compatibility and performance of 

materials for use in sealing applications involving exposure to solvent fluids. 

The volume increase (or swell) associated with the wetted specimens is an important parameter used to 

gauge the performance of a material for use with solvents. The level of swell is a measure of the solubility 

of the elastomer (solute) with the solvent (fluid). High swelling is a concern for several reasons. 

1. Swelling indicates that the test fluid can easily permeate into and out of the elastomer. Therefore the 

seal does not serve as an effective barrier and the solvent may leak out, either as a fluid or gas. 

2. High permeation (or high solubility) means that the elastomer (or a component of the elastomer) is 

more susceptible to dissolution and removal, otherwise known as leaching. 
21 

3. Excessive swelling may force the seal to extrude from the joined interfaces, thereby reducing the seal 

pressure of the elastomer. The extruded portion of the elastomer is also susceptible to damage via 

abrasion and tearing.

The volume and mass change after drying indicates the extent to which the test fluid was able to dissolve 

and remove the elastomer and/or its components. If the dried volume is significantly less than the initial 

volume, then not only is the sealing pressure reduced but gaps may form between the seal and the 

interface, resulting in an open path to leakage. A reduction in the mass also means that material is lost, 

and if one or more components are leached out, the physical properties, such as hardness, may change as 

well. 

The durometer hardness test measures the depth of an indentation (in a material) that is created by a given 

force. As such it is used to evaluate a material’s resistance to permanent indentation. There are several 

different scales used with the durometer depending on the material type. For soft materials, like the 

rubbers used in this study, the A scale is used and the protocol is outlined in ASTM D2240 type A scale. 

The Shore A hardness measurement can be used with either wet or dry specimens. In this study, the 

specimens were measured for hardness in the wetted state and after being dried for 20 hr at 60°C. For 

each test, the hardness was measured at five locations on each specimen and averaged for a final value. 

The change in wetted hardness was recorded to determine the hardness decrease (softening) that had 

occurred when the elastomers were completely soaked with the test fuel. Softening results in a decrease in 

the sealing pressure caused by relaxation of the elastomer and may subsequently lead to leakage. Also 

when a substantial drop in hardness is accompanied by a large swell in volume, the elastomer will extrude 

more easily past the contact surfaces, thereby further increasing the risk of leaking. If, after drying, the 

hardness is increased from the original condition, then embrittlement has occurred. Embrittlement will 

increase the chance of fracture, which can cause the seal to fragment and fail under the sealing load, 

thereby creating a leak. 

The third set of tests performed on the elastomers were DMA measurements, which are used to assess 

damping and stiffness of materials over a range of temperatures.33 The storage modulus (Eʹ) is measured 

as a function of temperature. Storage modulus is a measure of material elasticity. It can be described as 

the ability of a deformed material to recover to its original state after being deformed. The storage 

modulus is highly dependent on the molecular state of the elastomer and can be used to determine the 

temperature at which an elastomer transitions from a stiff glassy state to a more pliable rubber state, as 

shown in Fig. 14. At low temperatures the polymer has a low free volume, which restricts molecular 

stretching, twisting, and bending, thereby making the elastomer glass-like, hard, and very stiff. When the 

temperature is slowly increased, the elastomer will expand until the free volume is such that relaxation 

(stretching, twisting, and bending) occurs and the resulting storage modulus drops by several orders of 

magnitude. In this state the elastomer is rubbery and viscous. The temperature at which the storage 

modulus drops suddenly is known as the glass-to-rubber transition temperature (Tg) and is usually 

referred to as the glass transition temperature. The glass transition temperature is associated with the 

critical free volume needed for molecular relaxation, above which the material is useful as a seal. Both Eʹ

and Tg are highly dependent on the molecular structure, and changes in these two parameters indicate that 

important structural changes within the elastomer have occurred. 

3.3.1 Sealants 

For the first experiment, RectorSeal was evaluated in Fuel C and CE25a. Subsequently, Gasoila E-Seal 

and RectorSeal plus Teflon tape were added to the stir chambers containing the CE25a and CE10a test 

fluids. The test methodology followed the ASTM D 6396 Standard Test Method for Testing of Pipe 

Thread Sealants on Pipe Tees, shown in the flow diagram (Fig. 15) depicting the entire specimen 
Fig.14. Typical DM

Fig. 1

22 

MA plot of storage modulus with temperature.

. 15. Schematic of sealant test protocol.
23 

preparation and test procedure. The test fixtures were submerged in the test fluid for the 4 week test 

period, after which the test fixtures were removed, drained, and allowed to dry for 24 hr before leak 

testing. The sealants were evaluated by attaching the compressed air line to the open end and submerging 

each fixture in a beaker of water. The air pressure was initially set at 20 psi and then increased in 10 psi 

increments (with a 2 min hold time) until either bubbling was visible or 100 psi pressure was reached. 

3.3.2 Test Fuels 

The fluids used in this study were aggressive formulations based on standards described in SAE J1681 for 

use in compatibility studies. The test fluids used in this study were based on Reference Fuel C 

(or Fuel C), which is a mixture of 50% isooctane and 50% toluene. Fuel C produces swelling in polymers 

that is indicative of highly aromatic premium grades of automotive gasoline. The reference ethanol used 

in this study is the aggressive ethanol formulation defined in the SAE standard. Aggressive ethanol 

contains NaCl, acetic acid, water, and sulfuric acid, and the amounts of these components used to make 

1.0 Liter of aggressive ethanol are shown in the Table 6. 

Table 6. Aggressive ethanol formulation 

Component Amount needed to make 1.0 Liter 

(g) 

CDA ethanol 816.0 

Deionized water 8.103 

Sodium chloride 0.004 

Sulfuric acid 0.021 

Glacial acetic acid 0.061 

The aggressive formulation is conservative by design but is representative of field conditions since 

organic acids such as formic and acetic acid are present in certain fuels, including ethanol. These acids 

can be formed in the production process of ethanol or created via oxidation during handling, transfer, and 

storage. Sulfuric acid is formed by the reaction of fuel-borne sulfur with ethanol and can be particularly 

corrosive to metals and polymers. Commercial gasolines contain varying amounts of sulfur, which is 

usually present as disulfides. Disulfides are converted to sulfonic and sulfuric acids in the presence of 

atmospheric oxygen and water. Since ethanol is miscible with water, ethanol fuel blends will also contain 

contaminants previously dissolved in the hydrous ethanol. Any soluble contaminants, such as sodium 

chloride, residing in the fuel delivery or tank infrastructure will be present in the ethanol blended fuel. 

Test fuels containing “C” in the nomenclature will have Fuel C as the base component, while the “a” 

refers to the “aggressive” ethanol formulation mentioned previously. Therefore a test fuel designated as 

CE10a will contain 90 vol % Fuel C plus 10 vol % aggressive ethanol. These test fuels are designed to 

simulate severe, real-world conditions. They are also intended to minimize the length of exposure 

necessary to rigorously evaluate materials while providing a standard method of testing fuel system 

materials. 

The test fluids selected for this investigation were Fuel C, CE10a, CE17a, and CE25a. Fuel C was 

selected as the control since it is representative of premium gasoline and is a standard test fluid widely 

used for studying material compatibility to gasoline. CE10a represents an aggressive formulation of E10, 

and as such, it can be viewed as a baseline test fuel since E10 is currently available in many, if not most, 

fuel dispensers. 

A major focus of this study was to assess the compatibility of dispenser materials with gasoline blends 

containing ethanol in excess of 10% by volume. Of immediate concern is the impact associated with the 

potential of E15 usage, and the further possibility of allowances to E25. Quality surveys on E10 have 
24 

shown that the actual ethanol content can vary up to 2% from pump to pump.34 Therefore, instead of 

using a CE15a blend, we formulated to CE17a in order to conservatively represent E15 in the field. This 

composition also matches the test fluid used in the NREL/UL dispenser study. CE25a was selected due to 

the existing potential for even higher future ethanol concentrations. 

4. RESULTS 

4.1 PERFORMANCE OF STIR CHAMBERS 

The dynamic stir chambers were successfully operated continuously near 60°C for each 28 day exposure 

period. Daily measurement of the fluid temperature showed that the fluid temperature was maintained at 

59 ±1°C. The temperature of the vapor region was less consistent and varied ±5°C for each case. The 

average daily headspace temperature for each test fluid was as follows. 

1. Fuel C: 48.9°C 

2. CE10a: 43.2°C 

3. CE17a: 48.7°C 

4. CE25a: 52.6°C

The stir chambers developed small vapor leaks near the lid bearing; however, at the end of the first set of 

exposure runs, very little actual fluid was lost, so the following exposure runs were maintained at ambient 

to maintain consistency. 

4.2 SPECIMEN ANALYSIS OVERVIEW 

For the metals, the primary concern is corrosion. Therefore, the metals were evaluated according to their 

mass loss and change in appearance (to determine whether pitting or surface passivation had occurred). 

On the other hand, elastomers are used to provide stable and durable leak-tight seals. Issues such as 

elasticity, volume swell, shrinkage, and dissolution determine whether an elastomer will adequately 

provide a stable and durable seal. The elasticity is assessed through hardness and DMA measurements, 

while shrinkage is due to volume and mass loss as a result of dissolution of the base polymer or additive. 

The selected DMA results are tabulated in Appendix D, and the complete curves are available upon 

request. Volume swell is of primary importance since it indicates the level of mutual solubility between 

the polymer and test fluid, which ultimately relates to the potential for dissolution and extraction. 

Increased hardness is also a measure of embrittlement, which leads not only to a loss of elasticity but also 

to cracking of the elastomer itself. The most straightforward compatibility assessment was sealant 

performance, which was determined solely by visual detection of leaking of air. Sealants are deemed to 

meet the standard if no bubbling is detected at pressures less than 80 psi. 

4.3 METAL COMPATIBILITY PERFORMANCE 

Consistent with the results observed from the initial testing, very little corrosion of any of the metallic 

coupons was observed in Fuel C, CE10a, CE17a, or CE25a. Coupons exposed to the vapor phase above 

each solution exhibited slight discoloration in some cases—particularly the brass and bronze coupons—

but no measurable weight loss above the routine scatter of the measurement was detected for any 

materials. 

Among the coupons immersed in the different test solutions, 1020 mild steel, 1100 aluminum, 201 nickel, 

and 304 stainless steel were found to be essentially immune to corrosion for the exposure conditions 

evaluated. This result is consistent with that of the initial assessment —that is, essentially no weight loss, 
25 

no discoloration, and no tendency toward localized corrosion under/near the crevice washers—and 

suggests that these materials are suitable for extended service in intermediate fuel blends of this type and 

are not strongly impacted by the concentrations of ethanol in gasoline at these intermediate levels. 

Also consistent with previous results,31 immersed coupons of cartridge brass, phosphor bronze, zincplated (galvanized) steel, and lead-plated (Terne) steel exhibited variable degrees of discoloration and 

minor corrosion product film formation. The highest corrosion rate observed was about 30 μm/year for 

the cartridge brass immersed in CE10a, and only one other material (bronze exposed to CE25a) exhibited 

a corrosion rate above 10 μm/year. These rates were calculated assuming uniform weight loss. In most 

cases, the absolute value of the corrosion rate based on weight loss calculations is slightly comprised of 

minor amounts of adherent corrosion product, which tend to introduce a small underestimation error in 

the corrosion rate calculation. But it should be noted that none of the coupons suffered a measureable 

change in thickness and the original machining marks or plating grain structure remained visible on the 

coupon surface following testing. Further, based on earlier testing,31 it is suspected that the corrosion rate 

of the copper-based materials decreases with extended exposure time. 

Besides the fact that only negligible corrosion was observed for the Fuel C immersions (<0.3 μm/year), 

there was no apparent trend associated with corrosion rate of any materials as a function of ethanol 

fraction in the fuel. For example, Table 7 shows the corrosion rates calculated from weight change for 

phosphor bronze coupons as a function of ethanol fraction in the test fuel. These results can be interpreted 

to mean that, for such low corrosion rates, there are subtleties associated with each exposure condition 

that influence the amount of corrosion preceding film formation, but that these values are uniformly low 

and near the limit of detection. 

Table 7. Annualized corrosion rates of phosphor bronze 

 Reference Fuel C CE10a CE17a CE20a CE25a 

Corrosion rate of bronze (μm/year) 0.2 6 4 3 13 

Figures 16–18 represent the post-exposure appearance of coupons of cartridge brass, phosphor bronze, 

and galvanized steel, respectively, resulting from the expanded testing. These images indicate the degree 

of discoloration and film formation associated with each exposure (other materials indicated far less, or 

even no, discoloration and film formation). As indicated by the planned interval test results,31 particularly 

for the copper-based alloys, these corrosion films form quickly upon exposure to fuel at elevated 

temperature and tend to be adherent to and protective of the substrate. 

X-ray photoelectron spectroscopy (XPS) was performed on representative coupon surfaces following 

testing (to compare with results from unexposed coupons) to assess the corrosion film thickness and 

composition as a function of ethanol content in the exposure environment. The corrosion film 

composition and thickness were not found to be substantially functions of the percent of ethanol in the 

fuel blends (~ 10, 17, 20, and 25%). In other words, the XPS results for a given material were 

indistinguishable and independent of ethanol concentration. Representative XPS results, shown in Fig. 19, 

were measured for cartridge brass exposed to CE25a. The plot reveals the composition of the corrosion 

product film as a function of depth from the surface (the film is incrementally sputtered from the surface, 

and the identity of released materials is distinguished by relative energy). As stated, the sputter profiles 

for cartridge brass exposed to CE10a, CE17a, and CE20a were indistinct from that shown in Fig. 19 for 

exposure to CE25a. 
26 

Fig. 16. Post-exposure appearance of the cartridge brass specimens 

following 28 days of exposure to vapor (~55°C) and liquid (60°C) in the 

indicated environments. 

Fig. 17. Post-exposure appearance of the phosphor bronze specimens 

following 28 days of exposure to vapor (~55°C) and liquid (60°C) in the 

indicated environments. 
27 

Fig. 18. Post-exposure appearance of the galvanized steel specimens 

following 28 days of exposure to vapor (~55°C) and liquid (60°C) in the 

indicated environments. 

Fig. 19. XPS results for cartridge brass following immersion in CE25a for 

28 days at 60°C. 

 
28 

While detailed analysis is quite complicated, a summary analysis of the information in Fig. 19 can be 

highlighted by a few key points. For example, the copper profile comprises two components—relative 

predominance of Cu0

/Cu+1 near the specimen surface that occurs in concert with relatively elevated sulfur 

present as a sulfide and a distinct component (Cu0

) representing primarily the bulk copper of the 

substrate. Taken together, this information suggests the outermost portion of the corrosion product film—

on the order of 100 nm—is predominantly copper sulfide (Cu2S). The source of the sulfur is not certain, 

but it seems likely to be from the modest addition of sulfuric acid to the aggressive fuel formulations. 

Deeper into the film (partially mixed with and mostly beneath the outermost surface layer), zinc and 

oxygen predominate concurrently, presumably as the oxide (ZnO). Approximately 800 nm into the 

surface film, the relative amount of copper has returned to the value expected within the base metal, but 

the relative amount of zinc at this location is less than that expected in the base metal by a factor of nearly 

two, suggesting preferential leaching of zinc to a depth somewhat greater than the corrosion film 

thickness. (Similar selective leaching of tin and formation of a near-surface sulfide were detected for the 

bronze specimens.) 

Note also that carbon is a ubiquitous contaminant on the extreme surface of all specimens that have been 

handled in air, but the relatively slow dilution of carbon from the film to a depth of perhaps 300 nm 

suggests some carbon incorporation into the film during its formation. The source of the carbon could be 

from degradation of the elastomers exposed with the metal coupons in the same solution environment 

during testing. In fact, small amounts of ZnO were detected on all metallic specimens following exposure, 

suggesting at least modest interaction of corrosion products from specimens containing zinc with those 

that do not results from interaction of dissolved species in the common test fluid. In any case, while there 

is no doubt some complicated solution chemistry and reactions occur on the surface of metallic specimens 

exposed to these fuel blends, these reactions appear limited to the extreme surface (on the order of 

1000 nm) and no functionally significant degradation was observed. 

None of the plated coupons—Cr-, Ni-, Pb-, or Zn-plated steels, Cr-plated brass, or Ni-plated aluminum—

revealed any readily observable discoloration/change or measurable corrosion (no weight loss, no 

pit/crevice initiation). Further, none of the plated coupons with substrates partially exposed revealed 

accelerated corrosion due to galvanic coupling between the plating material and substrate. Weight 

changes for each of the partially exposed coupons were found to be directly related to the area fraction of 

the exposed substrate and the substrate identity. For example, the weight loss for a chromium-plated brass 

specimen with 30% of the chromium plating removed was found to approximate 30% of the mass loss of 

a completely bare brass coupon (leaving zero mass loss associated with the intact coating). Figure 20 

records the post-exposure appearance of the chromium-plated brass coupons with the substrate partially 

removed, and this result is representative of the pattern observed on all specimens with partially removed 

coatings. 

4.4 ELASTOMER COMPATIBILITY PERFORMANCE 

4.4.1 Fluid (Liquid) Exposures 

The Parker O-Ring Handbook provides a compatibility rating for the elastomers used in this study with 

the individual test fluid constituents.20 A summary of the compatibility ratings is listed in Table 8. In the 

Parker rating system, 1is satisfactory, 2 is fair (generally acceptable for static seal), 3 is doubtful 

(sometimes acceptable for static seal), and 4 is unsatisfactory. 

According to the Parker O-Ring Handbook, only fluoroelastomers (fluorocarbon and fluorosilicone) are 

deemed acceptable for o-ring applications using the test fuels examined in this study. Likewise, neoprene, 

SBR, and silicone are not considered satisfactory for standard gasoline use. Yet, new and used fuel 

dispenser systems feature all of these materials for E0 and E10 use. However, because the solvents listed 
29 

Fig. 20. Post-exposure appearance of the chromium-plated brass 

specimens following 28 days of immersion in the indicated environments. 

Table 8. Parker elastomer compatibility rating for o-ring applicationsa

Solvent NBR Fluorocarbon Neoprene SBR Polyurethane Fluorosilicone Silicone 

Gasoline 1 1 4 4 2 1 4 

Isooctane 1 1 2 4 2 1 4 

Toluene 4 1 4 4 4 2 4 

Ethanol 3 3 1 4 4 1 2 

Acetic acid 2 2 4 2 4 2 1 

Sulfuric acid 3 3 1 1 4 1 2 

a

Parker O-Ring Handbook, ORD 5700, Parker Hannifin Corporation, Cleveland, Ohio. 

in Table 8 were not tested as mixtures, those results cannot be used to precisely assess compatibility of 

blends of these solvents. In order to accurately assess material compatibility, it is necessary to expose the 

material specimens to test fluids composed of the appropriate concentrations of the components listed in 

Table 8. 

As discussed previously in the Introduction section of this report, the Parker rating system is solely based 

on volume swell and does not take into consideration other physical properties (shrinkage, hardness, etc.) 

affecting seal compatibility and performance. This study intended to measure as completely as possible 

the physical properties relevant to sealing. The changes in these properties that occur with exposure to the 

test fluids will augment the existing body of knowledge on the compatibility of ethanol with various 

infrastructure materials. 

All of the elastomer specimens that were exposed to the test fuels exhibited some level of volume swell. 

Even the Fuel C test fuel produced significant swelling. This fact indicates that some level of solubility 

existed with the elastomers and the test fluids. In fact, as shown previously in Fig. 3, the total solubility 

parameter of E0 is not far removed from the range of solubility parameters for most of the elastomer 
30 

samples, which were obtained from various solubility studies.35–40 Also shown in Fig. 3, the solubility 

matchup becomes more aligned as the ethanol concentration is increased, and for CE25a, the Total 

Hansen Solubility Parameter closely matches that of many of the elastomers, which indicates an increased 

potential for degradation via dissolution and extraction. The penetration or dissolution of the fuels into the 

elastomer enables the solvent to extract or remove the base polymer (in some cases) or remove any 

additive agents used as plasticizers, antioxidants, etc. Most elastomers (especially NBR and SBR) are 

compounded with additives to impart plasticity and durability, both of which are important sealing 

properties. 

The results show that the elastomers largely group together by material class as shown Fig. 21 for volume 

swell and wet hardness. Interestingly, volume swell was observed in all samples for the Fuel C exposures, 

and with the exception of polyurethane and the NBR rubbers, ethanol had no measureable effect on the 

drop in hardness. The fluorocarbons and fluorosilicone exhibited the lowest volume swell and drop in 

hardness; the level of swelling was less than 20%, which is usually considered the upper limit for many 

dynamic sealing applications for o-ring materials. For static applications, swelling up to 50% is generally 

considered acceptable.20 

Fig. 21. Decrease in hardness as a function of volume swell and ethanol 

concentration for each elastomer type evaluated. 

When exposed to Fuel C, the NBRs (except for NBR#3) and polyurethane swelled approximately 20% 

(the upper acceptable limit for many dynamic sealing applications). However, the addition of ethanol 

subsequently pushed the swell to 30% or higher. The hardness results for the fluorocarbons, 

fluorosilicone, NBRs, and polyethylene decreased with increased volume swell; the other elastomer types 

did not show a noticeable trend between wet hardness and swell. Especially noteworthy is the fact that the 

NBRs and polyurethane exhibited an additional 10 point drop in hardness with exposure to ethanol. This 

drop is significant and means that these samples will exhibit a greater tendency toward relaxation and 

reduced sealing pressure for ethanol-bearing fuels. It is important to note that the swell and hardness 

results for NBR#3 did not group with the other NBRs. In fact NBR#3 did not swell or soften to the same 

degree as the other NBRs. NBRs have a wide range of properties depending on the additives, copolymer 

-60.0

-50.0

-40.0

-30.0

-20.0

-10.0

0.0

0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0

Point Change in Wet Hardness

Wet Volume Swell, percent

Fuel C

CE10a

CE17a

CE25a

SBR

Silicone

Neoprene

Fluorocarbons

& Fluorosilicone

Polyurethane

NBRs

NBR#3
31 

ratio, degree of crosslinking, and processing. Therefore, it is not prudent (at this point in time) to 

generalize about the performance of NBRs other than to state that the range of properties is high and is 

dependent on many factors. 

Neoprene swelled between 60% and 80%, while SBR and silicone rubbers expanded by more than 120% 

(except for SBR exposed to CE25a). This excessive swelling will potentially result in extrusion of 

neoprene, SBR, and silicon seals through the adjoining surfaces, thereby resulting in a loss of material 

available for compression against the adjoining faces. For SBR the swelling is also accompanied by a 

roughly 50 point drop in hardness; the combination of high swell and drop in wet hardness means that 

SBR is the elastomer most susceptible to extrusion. 

Since swelling is a measure of solubility between the test fuel (solvent) and the elastomer (solute), mass 

loss, and therefore shrinkage will occur (following dry-out) if the test fuels did, in fact, dissolve and leach 

out elastomer components (either the base polymer or additives). The end result would be a decrease in 

mass and volume (shrinkage). The results presented in Figs. 22 and 23 show the effects of volume swell 

on the mass loss and shrinkage after drying for each elastomer for each test fluid. As expected the 

groupings are similar for mass loss and dried volume when plotted against the wetted volume swell. (In 

fact Fig. 24 shows an almost linear correlation between mass loss and dried volume change.) Upon 

drying, each of the eight fluoroelastomers had a slight mass and volume gain compared to their original 

unexposed condition. This increase is the result of incomplete removal of the test fuel in these specimens 

after drying and is an indicator that negligible dissolution and leaching occurred for the fluoroelastomers. 

The fluorosilicone rubbers experience a slight loss of mass and volume, but not enough material leached 

out to be considered significant. Interestingly, silicone rubber lost around 2% of its original mass and 4% 

of its original volume, even though the volume swell for this material was the highest measured (more 

than 120%). The SBR, NBR, polyurethane, and neoprene rubbers exhibited large shrinkages and mass 

Fig. 22. Mass change of elastomers after drying compared to the initial 

baseline condition as function of volume swell and test fluid. 

-16.0

-14.0

-12.0

-10.0

-8.0

-6.0

-4.0

-2.0

0.0

2.0

4.0

0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0

Dried Mass Change, percent

Wet Volume Swell, percent

Fuel C

CE10a

CE17a

CE25a

Fluorocarbons

NBRs

Neoprene

Silicone

SBR

Fluorosilicone

Polyurethane

Mass gain

Mass loss
32 

Fig. 23. Dry volume change of elastomers compared to the initial baseline 

condition as a function of volume swell and fuel type. 

Fig.24. Correlation between dry volume change and dry mass change. 

-25.0

-20.0

-15.0

-10.0

-5.0

0.0

5.0

10.0

0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0

Dried Volume Change, percent

Wet Volume Swell, percent

Fuel C

CE10a

CE17a

CE25a

Fluorocarbons

Fluorosilicone Silicone

Polyurethane

SBR

Neoprene

NBRs

Expansion

Shrinkage

-25.0

-20.0

-15.0

-10.0

-5.0

0.0

5.0

10.0

-20.0 -15.0 -10.0 -5.0 0.0 5.0 Volume change (following drying), %

Mass Change, percent

Fuel C

CE10a

CE17a

CE25a

Fluorocarbons

Fluorosilicone

Silicone

Neoprene

SBR, NBR &

Polyurethane

Expansion

Shrinkage

Mass loss Mass gain
33 

losses. The majority of the samples experienced greater than 10% shrinkage and greater than 7% mass 

loss. These values are considered high and would not be considered acceptable for most sealing 

applications. Note that neoprene experienced the highest levels of shrinkage (~17%) and mass loss 

(~15%). 

The change in hardness after drying from the initial state is important because any increase in hardness 

over the baseline condition represents embrittlement of the material. Dissolution and removal of 

plasticizers would greatly affect hardness; however, loss of the base polymeric material should not have 

too much of an effect on the final hardness values since it is not dependent on volume or mass. In fact 

when point change in dry hardness is plotted against mass change (Fig. 25) and dry volume change 

(Fig. 26), significant embrittlement is only observed for the NBR samples and neoprene. Interestingly, the 

dry hardness of polyurethane (specimens exposed to aggressive ethanol) does not group with the NBR 

samples as it had with earlier property changes. In fact polyurethane (when exposed to aggressive 

ethanol) is the only elastomer exhibiting a decrease in hardness along with a decrease in mass, an 

indication that the molecular structure had degraded. Because softening only occurred for the specimens 

exposed to ethanol, it seems likely that one or more aggressive components were able to react with the 

polyurethane. In fact Table 8 shows that polyurethane is the least compatible of the rubbers with ethanol, 

acetic acid, and sulfuric acid. The fluoroelastomers (which includes the eight fluorocarbons and one 

fluorosilicone sample) also experienced a small decline in hardness, which is likely an artifact of the 

residual fuel present in the polymer, as demonstrated by the slight increase in dried mass. The final 

hardness values for the SBR, silicone, and fluorosilicone rubbers were not greatly changed. The 

embrittlement associated with NBR and neoprene is likely the result of the leaching out of the 

plasticizers, such as phthalates, resulting in mass loss and shrinkage. NBRs most always contain 

plasticizers to improve flexibility and durability. The results also indicated that Fuel C was responsible 

for the embrittlement of these polymers as ethanol did not noticeably add to the increase in hardness. 

Fig. 25. Change in hardness (after drying at 60°C for 20 hr as a function of 

the change in dry mass). 

-15

-10

-5

0

5

10

15

20

-20.0 -15.0 -10.0 -5.0 0.0 5.0 Point Change in Hardness (Dry)

Percent Mass Change

Fuel C

CE10a

CE17a

CE25a

Fluorocarbons

Silicone

SBR

NBRs

Neoprene

Polyurethane

NBR#3

Fluorosilicone

Harder

Softer

Increasing mass loss
34 

Fig. 26. Change in hardness (after drying at 60°C for 20 hr as a function of 

the change in dry volume). 

The DMA results and curves for each specimen are shown in Appendix B and Appendix C, respectively. 

DMA results are important since they provide an assessment of the elastomer performance as a function 

of temperature. DMA measurement is highly sensitive to molecular changes of a polymer and is typically 

used to assess the degree of cure or crosslinking. Many dispenser elastomer materials undergo a 

significant change in properties from 0 to 50°C, which is typical of the temperature range of actual use. 

Thermal transitions in polymers can be described in terms of free volume, which is defined as the space a 

molecule has for internal movement and has been shown to be related to penetration of solvent. However, 

the DMA instrument used in this study was limited to dry operation and solvent penetration effects 

necessitate wet testing. 

The data yielded from the curves (see Appendix B) include the storage modulus (Eʹ), loss modulus (Eʺ), 

tan delta (ratio of Eʺ/Eʹ), and the temperatures associated with changes and peaks associated with the 

storage and loss moduli. A typical DMA result is a plot of log scale storage modulus with temperature as 

depicted in Fig. 14. At low temperatures (usually <0°C for elastomers), the storage modulus is high 

(1,000 to 10,000 MPa). At these temperatures, the elastomer is very stiff and behaves like a glass. In this 

glassy region, the free volume is low and the molecule is tightly compressed, which prevents additional 

molecular motion. At these temperatures, an elastomer may be unsuitable for use as a seal. As the 

temperature is increased, the expanding volume will reach a critical point, at which large segments of the 

molecule chains are able to move (via stretch, bending, and rotation), causing the storage modulus to drop 

to around 10–100 MPa. The temperature at which this begins to occur is the glass transition temperature 

(Tg). The Tg is normally the most significant transition of a polymer as the physical properties change 

drastically from a hard glassy to a rubbery state. The onset of the decrease in storage modulus is often 

referred to as the brittle point, which has been shown to correlate to brittleness, toughness, impact 

strength, fatigue, aging, strength, and rigidity. The storage modulus (at Tg), along with Tg, provides an 

ideal means for single temperature quality analysis that is sensitive to molecular polymerization. For 

rubbers, Tg also represents the lower operating temperature. Changes in Tg are used to monitor changes in 

-15

-10

-5

0

5

10

15

20

-25.0 -20.0 -15.0 -10.0 -5.0 0.0 5.0 10.0 Point Change in Hardness

Volume Change After Drying, percent

Fuel C

CE10a

CE17a

CE25a

Silicone SBR

Neoprene

Fluorosilicone

Fluorocarbons

NBRs

Polyurethane

NBR#3

Harder

Softer

Shrinkage Expansion
35 

the polymer, including plasticizer removal caused by solvents. Any increase in Tg resulting in exposure to 

the test fluid would indicate removal of a plasticizer additive and would effectively reduce the operational 

temperature range of the elastomer. The rubber plateau can also be used to assess plasticizer effects and is 

important since many of the additives compounded with rubber are designed to function in this region. 

The changes in onset storage modulus (onset Eʹ) as a function of the dried mass change are shown in 

Fig. 27. The onset Eʹ values can be used to assess elastomer–solvent interactions; however, the results 

show a wide variation in values for each elastomer type. For most of the fluorocarbons, the storage 

moduli varied ±10%, and there was little correlation between ethanol content and mass loss. Similar 

results were obtained for fluorosilicone and silicone rubbers. On the other hand, onset Eʹ was increased 

for polyurethane, SBR, and neoprene. An increase in Eʹ will manifest as an increase in stiffness or 

hardness, which in turn correlates to embrittlement and loss of durability. For most of the NBR samples, 

the onset Eʹ measurements had increased; however, in some cases Eʹ actually decreased.

The increased dry mass of the fluorocarbon specimens suggests that small amounts of test fluid remained 

in the molecular channels. However, we would expect any residual fuel to decrease the onset Eʹ in all 

cases, which was not observed to be the case. As mentioned previously, several of the NBR specimens 

showed a decline in the onset Eʹ. The hardness results are shown in Figs. 25 and 26, which indicate 

embrittlement of the NBR specimens after exposure to the test fluids. Since hardness and storage modulus 

are both measurements of elasticity, they should correlate with each other; however, the onset Eʹ did not 

correlate closely with the dry hardness results. Therefore, the onset Eʹ may not be a suitable measurement 

for assessing compatibility effects. 

It is important to consider that the hardness values were taken at room temperature, where the material is 

transitioning to rubber, whereas the onset Eʹ was measured at much lower temperatures (in the glassy 

region). The free volume and molecular arrangement of the elastomers in rubber and glassy regions is not 

the same, and therefore, the correlation may not be valid. A more comparable approach is to measure the 

storage modulus at a temperature close to where the hardness was measured. When the Eʹ values were 

Fig.27. Change in onset storage modulus as a function of dry mass change. 

-40

-20

0

20

40

60

80

100

-16.0 -14.0 -12.0 -10.0 -8.0 -6.0 -4.0 -2.0 0.0 2.0 4.0

Change in Storage Modulus, percent

Mass change, percent

Fuel C

CE10a

CE17a

Neoprene CE25a

NBRs

SBR

Silicone

Fluorosilicone

Fluorocarbons

Polyurethane
36 

measured at 25°C (Eʹ25), they were found to correlate to the hardness data, as shown in Fig. 28. The 

correlation between change in hardness and Eʹ25 was approximated by the curve shown, although the results 

for NBR#3 did not follow this relationship. This result is consistent with other data that showed that NBR#3 

did not group with the remaining NBRs. The results indicated that the margin of change in Eʹ25 was much 

greater that the corresponding change in hardness, indicating that Eʹ25 is more sensitive to solvent effects 

than dry hardness. The dependency of Eʹ25 on the test fluid ethanol content for each elastomer sample is 

further shown in Fig. 29. The materials exhibiting the largest increase in Eʹ25 were the NBRs and neoprene, 

while the fluorocarbons showed a decrease in Eʹ25 for the fluid exposures. Fluorosilicone, SBR and silicone 

were unaffected. As with hardness, dry-out mass, and shrinkage results for polyurethane, Eʹ25 was 

unaffected by Fuel C but was significantly reduced by the addition of ethanol. In contrast, ethanol had little, 

if any, effect on the Eʹ25 for neoprene. Interestingly, except for SBR and neoprene, the lowest Eʹ25 results 

were observed for the CE17a test fluids. This observation corresponds to the maximum level of swelling 

that occurred for these materials, which also occurred for the CE17a exposures. For the fluoroelastomers 

and NBRs, the Eʹ25 results for CE25a were nearly the same as those for the Fuel C results. 

Similar behavior was observed for the shift in the glass transition temperature as shown in Fig. 30. For the 

fluorocarbons, Fuel C was observed to reduce the glass transition temperature (between 5 to 10°C). The 

glass transition temperature was further reduced for the fluorocarbons with the addition of ethanol. The 

expanded dry volume for the fluorocarbons would be expected to raise the molecular free volume thereby 

initiating molecular relaxation at a lower temperature than the original condition. In contrast the test fluids 

increased Tg for the NBRs and SBR, and the Fuel C test fluid caused the highest level of shift for this 

elastomer type. The probable extraction of plasticizers is one explanation; however, the addition of 

ethanol actually lowered the Tg from the Fuel C result. If plasticizer extraction alone resulted in the 

increase in Tg, then it should increase further with the addition of ethanol, especially since the volume 

swell increased another 30% over the Fuel C exposures. This result suggests that some level of structural 

change is likely taking place in the NBR and SBR samples, and it appears as though the ethanol exposure 

may serve to increase the molecular free volume for NBRs and SBR. 

Fig. 28. Correlation of the change in hardness and the storage modulus 

when measured at 25°C. 

-15

-10

-5

0

5

10

15

20

-180 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120

Point Change in Dry Hardness

Percent Change in Storage Modulus at 25oC

Fuel C

CE10a

CE17a 

CE25a NBRs

Neoprene

SBR

Fluoroelastomers

Polyurethane

NBR#3

Silicone

Decreasing elasticity Increasing elasticity
37 

Fig. 29. Percent change in the storage modulus at 25°C for each elastomer 

sample. 

Fig. 30. Shift in the onset glass transition temperature Tg from the initial 

baseline condition. 

-15

-10

-5

0

5

10

15

20

Percent Change in Storage Modulus at 25oC

Fuel C

CE10a

CE17a 

CE25a

SBR

Silicone

Polyurethane

Neoprene

Fluorocarbons NBRs Fluorosilicone

-20

-15

-10

-5

0

5

10

15

20

25

Shift in Glass Transition Temperature, oC

Fuel C CE10a CE17a CE25a

Fluorocarbons

Fluorosilicone

NBRs

Polyurethane

Neoprene

SBRSilicone
38 

4.4.2 Vapor Exposures 

The vapor-exposed specimens were measured only for dry hardness and dry DMA properties. The 

headspace chemistry is expected to affect those properties relevant to sealing since the solvent vapors can 

also permeate into the elastomers and produce swell. The point change in hardness for the specimens in 

the vapor region was observed to correlate to the dry hardness changes of the fluid-exposed specimens, as 

shown in Fig. 31. The results show that the vapor-exposed specimens of NBRs and neoprene experienced 

significant embrittlement (hardness increase) but not as much as that for the liquid-exposed specimens. 

One interesting feature is that, in contrast to the liquid exposed-specimens, the vapor-exposed samples 

showed a significant increase in embrittlement with exposure to CE10a and CE17a. This result suggests 

that the chemistry of the vapor phase was significantly different from the liquid phase. In field 

installations, the vapor regions would be expected to have a higher concentration of both isooctane and 

ethanol relative to the toluene, and subsequently, a higher solubility with the exposed gases may be the 

case in many instances. 

Interestingly the shift in Tg associated with the vapor-exposed specimens correlated well with the fluidexposed specimens (Fig. 32). Likewise, the storage modulus at 25°C showed a roughly linear relationship 

between the vapor- and fluid or liquid-exposed specimens for each material and test fluid, in spite of the 

variability (scatter) of the data (Fig. 33). However, it is interesting to note that Eʹ25 results for the fluidexposed specimens were considerably lower than the results for the vapor-exposed specimens, and thus 

deviated from the general trend. This observation is important since it shows that NBRs can exhibit a 

wide range of properties, depending on their particular formulation. The results clearly show that the test 

fluid vapors impact the performance of the elastomers, albeit to a lower degree. Therefore, it is important 

to consider the compatibility of the elastomers to the vapors as well as the fluids. 

Fig. 31. Point change in hardness comparison between vapor- and fluidexposed specimens. 

-15

-10

-5

0

5

10

15

20

-15 -10 -5 0 5 10 15 20

Point Change in Hardness (Vapor)

Point Change in Hardness (Fluid)

Fuel C

CE10a

CE17a

CE25a

Polyurethane & Fluorocarbons

SBR, Fluorosilicone &

Silicone

NBRs & Neoprene

Softer Harder

Harder

Softer
39 

Fig. 32. Shift in Tg comparison between vapor- and fluid-exposed specimens. 

Fig. 33. Shift in storage modulus at 25°C comparison between 

vapor- and fluid-exposed specimens. 

-15

-10

-5

0

5

10

15

20

25

-20 -15 -10 -5 0 5 10 15 20 25

Shift in Tg from Baseline (Vapor), oC

Shift in Tg From Baseline (Fluid), oC

Fuel C

CE10a

CE17a

CE25a

-200

-150

-100

-50

0

50

100

150

-200 -150 -100 -50 0 50 100 150

Percent Change in E'(25) for Vapor 

Exposures

Percent change in E'(25) for Fluid Exposures

Fuel C

CE10a

CE17a 

CE25a

NBR#3
40 

4.5 SEALANT COMPATIBILITY PERFORMANCE 

The results in Fig. 34 show that the RectorSeal sealant passed for Fuel C. However, leaking was observed 

almost immediately at pressures less than 20 psi for the specimens exposed to CE10a and CE25a. These 

results indicate that the RectorSeal alone may not be compatible with ethanol-blended fuels. However, 

when Teflon tape is used with the RectorSeal product, leaking did not occur when exposed to CE10a and 

CE25a. The Gasoila E-Seal product also was observed to successfully pass the leak test by meeting the 

performance criteria for exposure to CE10a and CE25a. 

Fig.34. Sealant test results. 

5. CONCLUSIONS 

5.1 METALS AND ALLOYS 

None of the metal or alloy specimens exhibited corrosion rates at noteworthy levels, including those 

galvanically coupled. This result is consistent with the low electrical conductivities measured for ethanolgasoline containing less than 25% ethanol. It is important to keep in mind that this study was performed 

using test fluids that maintained water within the ethanol-fuel phase. Phase separation of the water (from 

the ethanol) did not occur. However, it is possible that phase separation may occur occasionally in actual 

use. Another noteworthy consideration is that the test coupons were unstressed, and there is some 

evidence that stress corrosion cracking may occur, in some instances.41 However, for unstressed metallic 

components exposed to single-phase test fluids, corrosion is not likely to occur from exposure to the test 

fluid alone. However, this may not be the case when the ethanol concentration exceeds 25 vol %. 

5.2 ELASTOMERS 

O-ring and seal manufacturers use the compatibility rating system mentioned previously to guide material 

selection for use in a particular fluid. This rating system is based solely on swell and does not consider 

other properties relevant to seal performance. The seal manufacturers take great pains not to define failure 

criteria for a particular rubber for the following three reasons. 
41 

1. For each elastomer type, there is a wide range of properties, depending on the processing conditions, 

degree of crosslinking, copolymer levels, additive types, and concentration. 

2. There are a wide variety of sealing applications. In fact there are almost as many different 

applications as there are seal types. O-ring usage is defined as either static or dynamic. The durability 

is highly dependent on the application, and there are a multitude of dynamic situations such as for 

pistons, valves, etc., requiring elastomer seals. Even for static face seals, pressure, temperature, 

lifetime, and even vibration are all factors that must be taken into consideration. 

3. The complexity and variety of elastomer formulations and applications mean that any failure criteria 

would have to be qualified for each of the many formulations, processes, and applications, and are 

beyond the original scope of this study. 

As a result, seal manufacturers will not warrantee their products based on any rating system. In fact the 

Parker O-Ring Handbook22 clearly states that it is the responsibility of users to field test any seals and 

o-rings prior to marketing their product. However, because existing elastomer–fluid compatibility data is 

quite limited, any additional information would be crucial to identifying potential compatibility problems. 

Additional analysis and correlation of these results to the field are necessary to fully understand and 

predict the impact of intermediate blends of ethanol on materials. 

In this study properties associated with wet and dried conditions were measured. Wetted properties 

included the volume swell and mass increase and hardness. These properties are important since volume 

swell (along with mass increase) is a measure of the mutual solubility of the elastomer and test fluid. All 

elastomers will typically exhibit some level of solubility with fluids. As the fluid or solvent is absorbed 

into the elastomer, there is a corresponding drop in hardness (softening). Wet hardness is important since 

it indicates how much softening of the elastomer is taking place during the exposure. Decreasing 

hardness, especially when combined with significant volume expansion, will also contribute to the ease of 

extrusion of a material. 

Most elastomers exposed to fluids will, at some point, undergo dry-out cycles as well. When the 

elastomer becomes dry, it will lose mass (and volume) if the solvent dissolves and extracts out one or 

more components during drying. The loss of mass and volume will increase the potential for leaking since 

a portion of the original seal is removed, thereby decreasing seal pressure. An elastomer compounded 

with plasticizers will also be susceptible to embrittlement (or increased hardness) and an overall loss of 

durability if the solvent is able to extract out the plasticizer components. Embrittlement will lead to 

decreased durability and increase the potential for cracking during shrinkage and use. Other additive 

compounds serve to improve durability by providing additional protection against ultraviolet radiation, 

ozone, and wear. Dissolution and removal of these compounds may not affect the physical properties but 

will reduce the elastomer durability and useful life. The dried properties (mass/volume change and 

hardness) provide critical information regarding the ability of the fluid solvent to dissolve and leach out 

one or more elastomer components. 

The physical properties measured for the elastomers (volume/mass change, wet and dry hardness, storage 

modulus, and Tg) were found to group together according to elastomer type. Even though several NBRs 

and fluorocarbon samples had different compositions and processing treatments, their physical properties 

generally fell within certain property groupings, especially for volume swell and hardness. The lone 

exception was NBR#3, which frequently did not group with the other NBRs. 

DMA measurement was useful for assessing solvent effects, especially the storage modulus (at 25°C) and 

glass transition temperature. The storage modulus is a measure of elasticity and was found to correlate 

well with the dry hardness. The glass transition temperature is important since it defines the lower 
42 

operational temperature limit for an elastomer. Both Eʹ25 and Tg showed particular sensitivity to the 

CE17a test fluid. 

5.2.1 Fluorocarbons 

Fluorocarbons yielded the lowest decrease in physical properties of the elastomers tested in this study. 

The addition of ethanol did not drastically affect the measured properties, and the eight fluoroelastomers 

exhibited only modest swell and softening (wet hardness decrease) upon exposure to the test fuels. The 

specimens swelled to around 20%, which is considered the upper limit for many sealing applications. 

Likewise the fluoroelastomers did not experience shrinkage and mass loss at the dried condition, nor did 

they become embrittled. Interestingly, the specimens exposed to the CE17a test fluid resulted in 

additional decreases in the glass transition temperature. 

5.2.2 Fluorosilicone Rubber 

The properties for the fluorosilicone rubber sample were found to be similar to the fluoroelastomer 

samples. Volume swell was relatively low (<30%). Fluorosilicone did experience a slight decrease in the 

dried mass and volume compared to the original condition, and the dry hardness was also increased 

slightly. However, the exceptionally low level of shrinkage and embrittlement that occurred is not 

considered significant and would indicate that fluorosilicone is acceptable as seal material for ethanol fuel 

blends. Interestingly, the Tg for fluorosilicone was relatively unaffected by fluid chemistry. 

5.2.3 Silicone Rubber 

The dried silicone sample lost only 2% of its mass and up to 4% of its original volume. In addition the 

hardness (after drying) was not altered significantly, indicating that embrittlement had not occurred. 

However, silicone did undergo the highest level of volume expansion (>120%) when exposed to the test 

fuels. This excessive swell, especially when combined with a corresponding 20 point drop in hardness, 

means that seal extrusion is an issue worth consideration, since any reduction of material between the 

joined interfaces will increase the probability of leaking. Another potential concern associated with the 

exceptionally high volume swell is the ease of permeation of the fuel through the elastomer. Fuel that can 

easily penetrate into the elastomer can also be easily released. All elastomers are susceptible to gas 

permeation, but the level of gas diffusion needs to be kept low. Additional permeability studies need to be 

performed on silicone prior to use in order to confirm its performance. 

5.2.4 SBR 

SBR experienced the highest combination of swell and softening. The volume expansion exceeded 90%, 

and hardness dropped 50 points when wet. The sample use in this study would not be considered 

compatible with many sealing applications of the test fluids. However, it is important to consider that 

SBR properties are highly dependent on additives, processing, and copolymer concentrations. This 

flexibility of design means that there may be appropriate formulations of SBR that will, in fact, meet a 

given sealing specification. 

5.2.5 NBR 

The eight NBR samples (and polyurethane) showed a pronounced increase in volume swell and softening 

when exposed to fuels containing ethanol. Exposures to Fuel C resulted in volume expansion approaching 

20%. When exposed to the ethanol-blended test fluids, the NBRs swelled by more than 30%. Likewise, 

the hardness values dropped an additional 10 points when ethanol was added to the test fluid. When all of 

the samples (including Fuel C exposures) were dried, 8% to 14% of the mass was lost and the 
43 

accompanying shrinkage was between 10% and 18%. The dried hardness was increased 5 to 16 points, 

indicating that embrittlement had occurred. NBR was one of only two elastomer types (the other being 

neoprene) that exhibited significant embrittlement in the dried state, indicating that plasticizer 

components were being removed by the test fuels. The results showed a high degree of variance, which is 

not surprising since NBR (like SBR) can be designed for a wide variety of applications. NBRs showed a 

significant increase in Tg with Fuel C exposure, but the addition of ethanol was observed to reduce this 

shift rather than extend it. Interestingly, the low volume expansion and reduced softening for the 

samples exposed to Fuel C suggest that these materials may in fact be acceptable for use in some E0 

gasoline applications. 

5.2.6 Polyurethane 

The polyurethane results essentially matched those of the NBRs, with one notable exception: 

Polyurethane became softer (not harder) when dried from the wetted state, but only for those samples 

exposed to ethanol; the hardness of the Fuel C exposures was unaffected. This result suggests that the 

polyurethane sample did not contain plasticizer additives. In fact, according to the Handbook of 

Elastomers,

42 polyurethane does not normally contain large levels of extractable components. However, 

the reduction in hardness (after drying) upon exposure to ethanol is noteworthy and suggests that the 

aggressive ethanol may have reacted with the polyurethane, causing permanent weakening. The poor 

wetted properties combined with the high shrinkage and mass loss indicate that polyurethane may not be 

an acceptable elastomer in many sealing applications for use with fuels containing up to 25% ethanol. The 

permanent weakening caused by exposure to ethanol is a potential concern. 

5.2.7 Neoprene 

The neoprene sample’s decrease in wet hardness was relatively low and was comparable to the results 

obtained for the fluorocarbons; however, the volume swell exceeded 60%, which may limit its use. 

Particularly disconcerting was the fact that neoprene exhibited the poorest dried properties of the 

elastomers tested in the study. Upon drying the mass and volume were reduced 15% and 20%, 

respectively. Neoprene also exhibited a high level of embrittlement, as the hardness was increased by 

14 points. The high mass loss and shrinkage, and the accompanying increase in hardness, suggest that 

neoprene (along with NBR) contained significant levels of plasticizers prior to the exposure runs. These 

plasticizer additives were removed by the test fuels, leaving the neoprene sample in a less durable 

condition. 

5.3 Vapor-Exposed Specimens 

The hardness and Tg results of the vapor-exposed specimens correlated with the results obtained for the 

wetted specimens of the elastomers tested. Embrittlement was observed for the NBRs and neoprene by 

vapors alone, which suggests that these materials need to be proven before being employed in vaporrecovery applications. The chemistry of the head space region will have higher concentrations of ethanol 

and isooctane relative to the toluene due to the volatility of these fuel components. It is reasonable to 

assume that this scenario will also occur out in the field. The exact concentrations of the fuel components 

were not measured, but we would expect that the solubility would change. 

5.4 Sealants 

The results show that although the standard PTFE sealant (RectorSeal) passed the ASTM D6396 criteria 

in Fuel C, the sealant experienced leaking at low pressures when exposed to either CE10a or CE25a. 

However, when RectorSeal was combined with Teflon tape, leaking did not occur. The results also show 

that the Gasoila E-Seal product maintained integrity in both Fuel C and CE25a up to 100 psi. The results 
44 

show that the standard PTFE sealants are not compatible without additional sealing brought about by the 

addition of Teflon tape. The Gasoila E-Seal product was successful at preventing leakage in CE25a 

according to the ASTM standard. 

6. REFERENCES 

1. Society of Automotive Engineers, “Gasoline, Alcohol, and Diesel Fuel Surrogates for Materials 

Testing,” SAE J1681, issued September 1993, revised January 2000-01. 

2. American Society for Testing and Materials, “Test Method for Testing of Pipe Thread Sealants on 

Pipe Tees,” ASTM D 6396 Standard. 

3. DOE/EIA Annual Energy Review 2008, DOE/EIA-0384(2008), June 2009, www.eia.doe.gov/aer. 

4. Energy Information Administration, EIA Energy Outlook 2009, DOE/EIA-0484(2009), May 2009, 

www.eia.doe.gov. 

5. U.S. Energy Information Administration, EIA Petroleum Supply Monthly, February 2009. 

6. U.S. Energy Information Administration, EIA Annual Energy Outlook 2010, December 2009. 

7. EPA-HQ-OAR-0211 and FLR-9215-5, October 13, 2010. 

8. Brent. D. Yacobucci, Intermediate-Level Blends of Ethanol in Gasoline, and the Ethanol “Blend 

Wall”, Congressional Research Service. October, 18, 2010. 

9. K. Boyce and J. T. Chapin, Dispensing Equipment Testing with Mid-level Ethanol/Gasoline Test 

Fluid: Summary Report, November 2010. 

10. D. W. Kirk, Fuel 62, 1512–1513 (December 1983). 

11. C. M. Hansen, Hansen Solubility Parameters: A User’s Handbook, 2nd Edition, CRC Press, Taylor 

& Francis Group, Boca Raton, Florida, 2007. 

12. B. H. West et al., Effects of Intermediate Ethanol Blends on Legacy Vehicles and Small Non-road 

Engines, Report 1, ORNL/TM-2008/117, October 2008. 

13. B. Jones, G.Mead, P. Steevens, and C. Connors, The Effects of E20 on Elastomers Used in 

Automotive Fuel System Components, Minnesota Center for Automotive Research, Minnesota State 

University, Mankato, February 22, 2008. 

14. G. Davis and C. Hoff, “The Effect of Using Ethanol-blended Gasoline on the Performance and 

Durability of Fuel Delivery Systems in Classic Automobiles,” SAE Paper No. 2010-01-2135. 

15. H. Jafari et al., Effect of Ethanol as Gasoline Additive on Vehicle Fuel Delivery System Corrosion, 

Materials and Corrosion 61(5), 432–440 (May 2010). 

16. R. F. Karg, C. L. Hill, K. Dosch, and B. Johnson, “Ultra-high CAN Polymer In Fuel System 

Application,” SAE 900196. 

17. L. Nihalani, R. D. A. Paulmer, and Y. P. Rao, “Compatibility of Elastomeric Materials with 

Gasohol,” SAE Paper No. 2004-28-0062. 

18. D. DiCicco, CRC AVFL-15 Project: E20 Durability Study Fuel System Components, presented to 

the Mid-level Ethanol Blends Research Coordination Group, May 5, 2010. 

19. Rubber Technology, 3rd Edition, Maurice Morton, Kluwer Academic Publishers, Norwell, MA, 

1999. 

20. Parker O-Ring Handbook, ORD 5700, Parker Hannifin Corporation, Cleveland, Ohio, 2007. 

21. P. A. Westbrook, Compatibility and Permeability of Oxygenated Fuels to Materials in Underground 

Storage and Dispensing Equipment, Oxygenate Compatibility and Permeability Report: A Technical 

Assessment of the Literature circa 1975–1997, State Water Resources Control Board Advisory 

Panel, January 1999. 

22. Dichtomatik O-Ring Handbook, D. Visscher, Editor, Dichtomatik North America, 47690 East 

Anchor Court, Plymouth, Michigan.

23. O-rings, Inc., http://www.oringsusa.com/html/compatibility.html 

24. Precision Polymer Engineering, http://www.prepol.com/ 
45 

25. P. Touchet, B. Zanadis, M. Fischer, and P. E. Gatza, Materials Compatibility Studies with 

Fuel/Alcohol Mixtures, Technical Report 2366, U. S. Army Mobility Equipment Research and 

Development Command, Fort Belvoir, Virginia, July 1982. 

26. A. Nersasian, “The Use of Toluene/Isooctane/Alcohol Blends to Simulate the Swelling Behavior of 

Rubbers in Gasoline/Alcohol Fuels,” SAE Paper No. 800790. 

27. I. A. Abu-Isa, “Effects of Mixtures of Gasoline with Methanol and with Ethanol on Automotive 

Elastomers,” SAE Paper No. 800786. 

28. G. Micallef and A. Weimann, “Elastomer Selection for Bio-fuel Requires a Systems Approach,” 

Sealing Technology, January 2009. 

29. R. D. Stephens, “Fuel and Permeation Resistance of Fluoroelastomers to Ethanol Blends,” ACS 

Technical Meeting of the Rubber Division, Cincinnati, Ohio, October 2006. 

30. A. Ertekin and N. Sridhar, “Performance of Elastomeric Materials in Gasoline-Ethanol Blends—

A Review,” Paper no. 09533, CORROSION 2009 Annual Conference and Exhibition, NACE 

International, Atlanta, Georgia. 

31. S. J. Pawel, M. D. Kass, and C. J. Janke, Preliminary Compatibility Assessment of Metallic 

Dispenser Materials for Service in Ethanol Fuel Blends, ORNL/TM-2009/286. 

32. American Society for Testing and Materials, “Test Method for Rubber Property-Durometer 

Hardness,” ASTM D 2240 Standard, 2005. 

33. K. P. Menard, Dynamic Mechanical Analysis: A Practical Introduction, 2nd Edition, CRC Press, 

Taylor & Francis Group, Boca Raton, Florida. 

34. NREL data sheet provided by Kristi Moriarty on January 13, 2011. 

35. A. Huba, L. Molnar, A. Czmerk, and T. Fischl, “Dynamic Analysis of Silicone Elastomers,” 

Budapest University of Technology and Economics. 

36. M. Kotal, S. K. Srivastava, and A. K. Bhowmick, “Thermoplastic Polyurethane and Nitrile 

Butadiene Rubber Blends with Layered Double Hydroxide Nanocomposites by Solution Blending,” 

Polym Int 59, 2–10 (2010). 

37. M. Myntti, “Comparing Fuel and Oil Resistance Properties,” Rubber World, June 1, 2003. 

38. N. M. Sammes, S. Vohora, and A. M. Carter, “Swelling Parameter of Polypropylene Used in 

Household Appliances,” Journal of Materials Science 29, 6255–6258 (1994). 

39. R. Guo, A. G. Talma, R. N. Datta, W. K. Dierkes, and J. W. M. Noordermeer, “Solubility Study of 

Curatives in Various Rubbers,” European Polymer Journal 44, 3890–3893(2008). 

40. R. Mieczkowski, “Solubility Parameter Components of Some Polyurethanes,” European Polymer 

Journal 28(1), 53–55 (January 1992). 

41. E. Voegele, “It’s not just a pipe dream,” Ethanol Producer Magazine, January 12, 2009, 

www.ethanolproducer.com/articles/5270/its-not-just-a-pipe-dream 

42. Handbook of Elastomers, 2nd Edition, A. K. Bhowmick and H. L. Stephens, editors, Marcel Dekker, 

Inc., New York, NY, 2001. 

APPENDIX A 

ORNL/UL POSTMORTEM ANALYSIS OF FACEPLATE RUBBER-CORK 

GASKETS USED IN NREL/UL DISPENSERS 1, 3, AND 5 

 

A-3 

APPENDIX A 

ORNL/UL POSTMORTEM ANALYSIS OF FACEPLATE RUBBER-CORK 

GASKETS USED IN NREL/UL DISPENSERS 1, 3, AND 5 

ORNL Investigators: Mike Kass, Tim Theiss, Sam Lewis, Chris Janke, Maggie Connatser, and 

Michelle Kidder 

UL Lead Investigator: Tom Chapin 

A postmortem study was performed on the rubber-cork faceplate gaskets for Dispensers 1, 3, and 5 from 

the UL/NREL study. The rationale for selecting gaskets from Dispensers 1 and 5 was that these 

dispensers were the only ones in which the fuel chemistry was measured periodically throughout the 

NREL/UL prototype tests. Both of these dispensers exhibited leaking at the faceplate gasket. Comparison 

of the fuel chemistry results to the postmortem analysis may provide information useful to the 

interpretation of failure mechanisms. It is important to note that Dispensers 1 and 5 were made by the 

same manufacturer; Dispenser 1 was a new dispenser, while Dispenser 5 was similar in design to 

Dispenser 1 and had been used for 5 years. Interestingly, all of the meter seals were cork impregnated 

with an elastomer. We employed several analytical techniques to characterize and identify the rubber 

fraction of each gasket. These methods included diffuse reflectance infrared transform (DRIFT) 

spectroscopic analysis, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and 

pyrolysis gas chromatography–mass spectrometry (GC-MS). 

The design of Dispensers 1 and 5 consisted of four faceplates mounted in a vertical arrangement using 

four bolts on each faceplate. In contrast, the housing seal for Dispenser 3 was held horizontally in place 

using six bolts and bore the weight of the top housing section, which was estimated to weigh around 5 kg 

(~10 lb). Accordingly, the faceplate gaskets for Dispensers1 and 5 had identical designs, but the gasket 

for Dispenser 3 had an entirely different layout. The gasket material for all three dispensers was 

rubberized cork. 

The appearance of the gaskets is noteworthy. The thicknesses of the gaskets were measured at the 

compressed region and at the interior edges, which were uncompressed and exposed to the test fuel. The 

thickness measurements are listed in Table A-1 and show that the Dispenser 3 gasket was much thinner 

than those of Dispensers 1 and 5. However, without knowing the starting thicknesses, it is impossible to 

ascertain the degree of compressibility or swelling. 

Table A-1. Thickness of the rubber-cork gaskets used as meter seals 

Dispenser gasket Thickness of surface area 

exposed to fluid (mm) 

Thickness of compressed 

surface area (mm) 

Dispenser 1 (new) 1.6 1.14 

Dispenser 5 (used) 1.66 1.34 

Dispenser 3 (used) 1.42 1.4 

Selected gasket sections are shown in Figs. A-1, A-2, and A-3. Visual observation of the three gaskets 

revealed several interesting features. The most noticeable was the black coloration of the Dispenser 3 

gasket elastomer compared to the gray coloration of the elastomer used in Dispensers 1 and 5. The black 

coloration is indicative of the carbon black, which is commonly added as a pigment and to improve 
A-4 

Fig. A-1. Housing gasket for Dispenser 3 (used), which passed the UL 87a tests. Dark regions are 

the elastomer, and the brown regions are the cork.

Fig. A-2. Faceplate gasket for Dispenser 1 (new), which failed the UL 87a tests. 

Outer (uncompressed) surface

Interior surface (exposed to fluid)

Outer (uncompressed) surface

Interior surface 

(exposed to fluid)
A-5 

Fig. A-3. Faceplate gasket for Dispenser 5 (used), which failed the UL 87a tests. 

elastomer wear and durability. The elastomer bonded to the cork (for Dispensers 1 and 5) either had very 

low levels or no carbon black additive. Further examination of the Dispenser 3 gasket surface showed 

very little degradation for the region exposed to the test fluid (Fig. A-1), and the elastomer component of 

the gasket was intact. In contrast, the region of Dispenser 1 (Fig. A-2) that was exposed to the test fuel 

was considered very weak, judging by the readiness at which the cork particles could be removed by 

gentle tugging; in contrast, the compressed section (which was not directly exposed to the test fuel) 

required much more force to tear. Visual observation indicated that very little elastomer remained in this 

section. Likewise Dispenser 5 (Fig. A-3) showed some degradation on the exposed gasket surface but not 

to the degree observed for Dispenser 1. It is important to note that although the gaskets used in Dispensers 

1 and 5 appear identical, Dispenser 1 was a new unit, while Dispenser 5 had 5 years of operational use. 

The absence of the elastomer component of the new dispenser (No. 1) in the fluid contact region is a 

strong indicator that the polymer was effectively dissolved by the test fuel and most likely caused the 

observed leakage during the testing procedure. 

Sections of each gasket were removed and evaluated for thermogravimetric analysis (TGA). During TGA, 

a pre-weighed section of the gasket was heated in air and the mass loss as a function of temperature was 

recorded. The results for the three gaskets are presented in Fig. A-4. Dispensers 1 and 5 gaskets exhibited 

nearly identical behavior, showing a large drop in mass around 300o

C, which is consistent with 

combustion of the polymer. The hydrocarbon removal for these gaskets was completed at 500o

C, and the 

final mass of the inorganic (noncombustible) portion was almost 35% of the original mass. In contrast, 

the Dispenser 3 gasket did not finish burning until 600o

C, and the final weight was closer to 22%. The 

results indicate a very high level of inorganic compounds within the gasket rubber portions of 

Dispensers 1 and 5 that was not present in the rubber fraction of Dispenser 3. Since pure cork typically 

combusts to a final mass percentage ranging from 5 to 15%, the remainder (which was at least 25%) must 

have originated in the rubber fraction itself. 

Outer (uncompressed) surface

Interior surface (exposed to fluid)

Waxy deposit
A-6 

Fig. A-4. TGA (in air) curves for rubber-cork gaskets used in Dispensers 1, 3, and 5. 

The inorganic residue from all three gaskets was analyzed for x-ray florescence, and the results showed 

that the inorganic fraction was predominantly silica. Silica is commonly added to elastomers to impart 

ultraviolet and heat resistance. 

The TGA results show that the rubber-cork gaskets used in Dispensers 1 and 5 were identical and that the 

gasket used in Dispenser 3 was significantly different. This difference was believed to be primarily 

limited to the elastomeric portion of the rubberized cork gaskets. 

DRIFT and DMA Analysis 

Each of the gaskets was sectioned and analyzed using diffuse reflectance infrared Fourier transform 

(DRIFT) spectroscopy and dynamic mechanical analysis (DMA). The DRIFT technique is useful for 

identifying functional hydrocarbon groups but cannot be used to identify specific plastic materials. DMA 

provides a modulus versus temperature curve, and that information provides a better means of identifying 

a particular polymer compound. The DRIFT analysis showed measurable amounts of isolated hydroxyls 

(-OH) in the gaskets for the two failed dispensers (1 and 5), while the gasket from Dispenser 3 did not. 

The presence of the isolated hydroxyls is a strong indicator that the elastomer compound in the cork seal 

had degraded. 

Pyrolysis GC-MS 

The rubber fractions of the cork gaskets were evaluated by UL using pyrolysis GC-MS to determine the 

type of rubber used in the cork. Analysis of gaskets from Dispensers 1 and 5 showed that the rubber 

64.21%

77.46%

20

40

60

80

100

120

Weight (%)

0 200 400 600 800 1000 1200

Temperature (°C)

 1.002 –––––––

 3.001 –––––––

 5.001 –––––––

Universal V4.7A TA Instru

#5 Gilbarco (used)

#1 Gilbarco (new)

#3 Tokheim (used)

Temperature(degrees Celsius)

Mass (%)

#3 (used)

#1 (new)

#5 (used)
A-7 

consisted of epichlorohydrin. Epichlorohydrin is an organochlorine compound that is considered soluble 

with most polar organic solvents. It has excellent resistance with nonpolar hydrocarbons such as gasoline, 

toluene, and isooctane but would be expected to have solubility with ethanol. Epichlorohydrin rubber 

(ECO) does not perform well in oxygenated gasoline and will revert towards the uncured product to 

become soft and devulcanized. This softening is indicative of a reaction of the epichlorohydrin with the 

test fluid. Because ECO is compatible with gasoline and hydrocarbon fuels, the softening (degradation) is 

most likely caused by the ethanol component of the test fluid. This assessment is supported by the DRIFT 

analysis, which showed that the rubber had oxidized. 

In contrast, the rubber fraction for the cork gasket used in Dispenser 3 (which did not leak) was found to 

be NBR. NBR is considered to be more compatible than ECO with ethanol and thus did not leak due to 

exposure. Based on these results, the incompatibility of ECO with ethanol is likely responsible for the 

leaking noted at the meter faceplates for Dispensers 1 and 5. The compatibility of the cork fraction was 

not assessed. The cork fraction was observed to swell upon exposure to the test fluid, but did not appear 

to physically degrade. Cork, by itself, is too weak to be used without a rubber matrix to impart the 

necessary strength and elasticity to form an effective seal. The results suggest that the rubber component 

is the critical component that determines whether the seal is effective or not. 

APPENDIX B 

ORNL DISPENSER STUDY USING RECIRCULATING CE25A 

AND CE85A TEST FLUIDS 

 

B-3 

APPENDIX B 

ORNL DISPENSER STUDY USING RECIRCULATING CE25A 

AND CE85A TEST FLUIDS 

ORNL Investigators: Mike Kass, Tim Theiss, Sam Lewis 

UL Investigators: Team: Ken Boyce, Tom Chapin, Tom Fabian, Joe Bablo 

BACKGROUND 

Underwriters Laboratories (UL) was interested in examining the corrosive potential of fuel dispenser 

components to ethanol-gasoline blends containing 25 and 85 vol % ethanol. UL had an ongoing program to 

evaluate corrosion in selected dispensers by exposing the components (filter, meter, valve, hose, nozzle, 

connectors, and tubing) to either CE25a or CE85a fuel compositions under static (noncirculating) 

conditions. However, it was felt that the data provided from the static experiments may not be applicable to 

a more realistic environment, whereby materials and components are exposed to moving fluid, rather than 

static exposure. In recognition of this need, the U.S. Department of Energy supported the National 

Renewable Energy Laboratory (NREL) and Oak Ridge National Laboratory (ORNL) to undertake a series 

of prototype dynamic experiments. The objective was to compare the dynamic results measured by ORNL 

and compare these results with the static results from the earlier UL tests. The results were to be used to 

assess whether static-based experimentation can adequately reflect the dynamic situation. 

DISPENSER COMPONENTS AND EXPERIMENTAL PROCEDURE 

Following a series of meetings, UL provided ORNL with two identical fuel dispensers to evaluate for this 

study. One dispenser was used to evaluate compatibility with E25 fuel (25 vol % ethanol), while the other 

was used to evaluate the compatibility with E85. The objective was to run a prototype dispenser system 

for both E25 and E85 fuels to understand the compatibility of these fuels with dispenser materials and 

components. The dispensers were operated for 15 weeks during the summer months of June, July, and 

August in order to capture the peak temperatures for 2007. The rate of reaction can frequently be inferred 

with the rate of corrosion and therefore roughly follows the Arrhenius Equation for the reaction rate with 

temperature. Therefore corrosion is directly related to temperature, and the peak temperatures associated 

with summer should provide an upper bound on the rates of corrosion for dispenser materials. 

At the conclusion of the 15 week exposure period, it was decided to continue with another 15 week 

exposure, which would capture the cold ambient conditions associated with the late fall and winter 

months. The dispensers were refilled with new CE25a and CE85a fuel compositions and operated until a 

pump failure occurred on January 24, 2007. 

The results from the ORNL dynamic experiments will be compared against those obtained from a series 

of static experiments performed by UL. The dispenser components consisted of a regulator-filter 

assembly, shutoff valve, hose, and nozzle. These components were assembled and installed in a covered 

area at the National Transportation Research Center (NTRC) facility by ORNL staff. The dispenser 

components were connected to a 55 gal 316 stainless steel drum, which served as the fuel storage tank. 

Each component was thoroughly grounded to prevent static discharge. The drum was also equipped with 

a flame arrester, and other safety features were added to minimize the potential for fire. Fig. B-1 shows 

the configuration of both dispenser assemblies, with labels added to one system for component 
B-4 

Fig. B-1. Photograph showing assembled and operating dispensers. The left and right units were used for 

the CE25a and CE85a fuels, respectively. 

identification. A block diagram of the dispenser system, including descriptions of key components, is 

shown in Fig. B-2. To enable continuous flow, the shutoff features of the solenoid valve and the nozzles 

were disabled. Underwriters Laboratories also provided two air-assisted diaphragm pumps to provide 

realistic fuel flow (around 8 gal/min). During operation, the fuel was pumped from the bottom of the tank, 

through the pump, and then through the dispenser assembly. The hose was connected to a stainless steel 

tube, which returned the fuel to the tank at a level well below the fuel surface (this setup helps to prevent 

the possible generation of static buildup caused by flow through the gaseous headspace). All of the 

components not considered in this study were composed of 316 stainless steel to prevent additional 

contamination. 

The two fuel types selected for the dispenser compatibility experiments were CE25a and CE85a. These 

formulations represent controlled simulations of E25 and E85. Instead of using pump-grade gasoline, the 

nonethanol component of the fuel consisted of equal parts of isooctane and toluene (Fuel C). A small 

quantity (0.8 vol %) of a weak acid solution was added to the ethanol portion to simulate impurities that 

may be present in pump-grade gasoline and accelerate the corrosion process. Approximately 40 gal were 

prepared for each fuel type. The flow rates for the CE25 and CE85a fuels were measured at 6.3 and 

7.9 gal/min, respectively. The reason for this discrepancy is unclear but may be related to viscosity 

differences in the fuel compositions. 

Hose

Nozzle

Drum

Meter

Valve

Strainer Pump

Fuel return

flow Hose

Nozzle

Drum

Meter

Valve

Strainer Pump

Fuel return

flow
B-5 

Fig. B-2. Schematic diagram showing the arrangement of the dispenser components. A brief description 

of the components is included.

The dispensers began operating on June 20, 2007. One-liter fluid samples were extracted once per week 

for the first two months and then every two weeks thereafter. A timeline showing fluid sample removal is 

shown in Table B-1. The removed fuel portion was not replaced during the course of this study. For each 

fluid sample the ambient and fuel temperatures (inside the drum) were measured every 30 min. The 

pumps were operated roughly 8 hours per day during the 5 day work week. 

The temperature profiles for both dispensers were nearly identical. Fig B-3 shows the temperature profile 

for the CE25a fuel dispenser. The data captures the diurnal cycles associated with ambient temperature 

changes from the day and night. During the period from June 20 to August 5, the ambient temperature 

(during the day) approached a maximum of 30o

C during the day and dropped to ~23oC during the 

evening. From August 5 through August 30, the daytime temperature peaked to around 35 to 37o

C and 

dropped to around 25o

C during the evening. This period had the hottest temperatures at the test site for 

2007. The data also show that (during the evening hours when the pumps were not operated) the fuel did 

not cool down to ambient temperatures, indicating that the mass of the stagnant fuel was sufficient to 

prevent rapid heat loss as the temperature dropped. The first 15 week period ended on October 5, 2007. 

As shown in Fig. B-4, the appearance of the fuels changed considerably over the course of the 15 week 

evaluation period. Initially, both fuel types were clear with a slight tint of pink coloration. After 6 weeks 

of pump operation, the CE25a fuel took on an amber color as shown in the photograph. In contrast, the 

CE85a fuel did turn amber but darkened with prolonged exposure as shown in Fig. B-4. Close-up 

inspection of the exposed CE85a fuel suggests that the dark tint may be caused by suspended particulates 

originating from the hose line. No darkening was observed for the CE25a fuel. 

Pump

Chim Tek Filtration

Bio-Tek microglass

Liqua-Tech meter

Model LPM-101E

Flexsteel hardwall

Gasoline hose

Goodyear 559N

OPW 11A

nozzle Stainless Steel Tubing

Stainless Steel Drum

SS Tubing

Steel Tubing

And fittings

Pump

Chim Tek Filtration

Bio-Tek microglass

Liqua-Tech meter

Model LPM-101E

Flexsteel hardwall

Gasoline hose

Goodyear 559N

OPW 11A

nozzle Stainless Steel Tubing

Stainless Steel Drum

SS Tubing

Steel Tubing

And fittings
B-6 

Table B-1. Timeline for fuel sample withdrawal 

Date Period Description 

June 20, 2007 First 15 weeks Began system operation 

June 29, 2007 First 15 weeks Fuel samples withdrawn 

July 10, 2007 First 15 weeks Fuel samples withdrawn 

July 17, 2007 First 15 weeks Fuel samples withdrawn 

July 24, 2007 First 15 weeks Fuel samples withdrawn 

July 31, 2007 First 15 weeks Fuel samples withdrawn 

August 7, 2007 First 15 weeks Fuel samples withdrawn 

August 14, 2007 First 15 weeks Fuel samples withdrawn 

September 18, 2007 First 15 weeks Fuel samples withdrawn 

October 2, 2007 First 15 weeks Fuel samples withdrawn 

October 12, 2007 – Fuel samples withdrawn (control samples) 

October 26, 2007 Second 15 weeks Fuel samples withdrawn 

November 9, 2007 Second 15 weeks Fuel samples withdrawn 

November 30, 2007 Second 15 weeks Fuel samples withdrawn 

January 22, 2008 Second 15 weeks Fuel samples withdrawn (end of study) 

Fig. B-3. Temperature profile for the CE25a dispenser during the first 15 week evaluation period. 

Temperature Profile for First 15 Weeks

0

5

10

15

20

25

30

35

40

45

2007-06-27

00:00:00

2007-07-07

00:00:00

2007-07-17

00:00:00

2007-07-27

00:00:00

2007-08-06

00:00:00

2007-08-16

00:00:00

2007-08-26

00:00:00

2007-09-05

00:00:00

2007-09-15

00:00:00

2007-09-25

00:00:00

2007-10-05

00:00:00

2007-10-15

00:00:00

Temperature, o

C

Ambient Temperature (°C)

Fluid Temperature (°C)
B-7 

Fig. B-4. Photograph showing the change in appearance (color) of the fuel 

types during the first (summer) 15 week exposure period. 

A second 15 week run was initiated to assess the influence of cooler temperatures and continued exposure 

of the dispenser components to the two fuel types. New batches of CE25a and CE85a were formulated on 

October 11, 2007, and on the following day (October 12, 2007) the pumps began operating. Fuel samples 

were drawn approximately every two weeks, and the dispenser pumps were operated until a pump failure 

occurred on January 24, 2008. The temperature profiles for the two dispensers during this period were 

also nearly identical; the profile for the CE25a dispenser is shown in Fig. B-5. The results show that the 

ambient (and fluid) temperatures steadily dropped over the course of the investigation and, prior to pump 

failure, the temperature had dropped below freezing for an extended period. The cause of the pump failure 

was identified as a fractured Teflon diaphragm, which is not a component under evaluation in this study. 

A discussion with the pump manufacturer revealed that these pumps were not rated for temperatures 

below 5o

C or 40oF. However, as can be seen in Fig. B-5, the pumps, in fact, were operated at temperatures 

well below the minimum temperature rating. The appearance of the fractured diaphragm indicated that the 

failure resulted from cold operation and was not influenced by the fuel whatsoever. 

The physical appearance of the CE25a and CE85a fuel types at several points during the second 15 week 

period is shown in Fig. B-6. In contrast to the first 15 week exposure, the color of the fuels did not change 

as dramatically over the course of the exposure period. The CE25a fuel did change noticeably from a light 

pink starting color to a light yellow coloration for the 2-week and 14-week sampling intervals. However, 

for these two sampling periods, the appearance for the CE85a did not change much during this time 

frame. The less dramatic fuel coloration for the second (winter) 15-week exposure may be due to the fact 

that relevant mass removal had already occurred during the summer exposure. The lower winter 

temperature may also be a factor, although the long exposure period means that sufficient permeation and 

dissolution should have occurred. 
B-8 

Fig. B-5. Temperature profile for the CE25a dispenser during the second 15 week evaluation period. 

Fig. B-6. Photograph showing the change in appearance (color) of the fuel 

types during the second 15 week exposure period. 

Temperature Profile for Second 15 Weeks

-10

-5

0

5

10

15

20

25

30

35

2007-10-05 00:00:00 2007-10-25 00:00:00 2007-11-14 00:00:00 2007-12-04 00:00:00 2007-12-24 00:00:00 2008-01-13 00:00:00 2008-02-02 00:00:00 Temperature, o

C

Ambient Temperature (°C)

Fluid Temperature (°C)
APPENDIX C 

COMPATIBILITY ASSESSMENT OF FUEL DISPENSER METALS AND 

ELASTOMERS IN AN AGGRESSIVE E20 FUEL 

 

C-3 

APPENDIX C 

COMPATIBILITY ASSESSMENT OF FUEL DISPENSER METALS AND 

ELASTOMERS IN AN AGGRESSIVE E20 FUEL 

ORNL Investigators: Michael Kass, Steve Pawel, Chris Janke, Tim Theiss, and Sam Lewis 

NREL Investigator: Wendy Clark 

UL Investigators: J. Tom Chapin, Ken Boyce, Tom Fabian, and Joe Bablo 

INTRODUCTION 

In this study the compatibility of selected metals and elastomers with an aggressive E20 fuel formulation was 

evaluated. The materials were exposed to the test fuel as individual specimens and not as a component or 

subsystem. The metals selected for the experiment covered those used in standard fuel dispenser hardware 

and included several grades of carbon and stainless steel, brass, bronze, and copper, while the elastomer study 

focused on fluorocarbons provided by DuPont and 3M. The metals were evaluated for mass loss and surface 

analysis, while the elastomeric materials were evaluated for tensile properties, hardness, and swelling. To 

facilitate compatibility phenomena, the specimens were placed in a specially designed chamber to enable 

dynamic fluid flow and maintain a constant elevated temperature of 60°C. The combination of dynamic flow 

coupled with elevated temperature (and aggressive fuel chemistry) offers the potential to get meaningful 

comparative results in a relative short time. The results of this study are expected to assess the compatibility 

of fuel dispenser materials and guide incorporation and integration of ethanol-resistant materials. 

EXPERIMENTAL METHOD 

Materials and Equipment 

Dynamic Test Chambers (Stir Tanks). To evaluate the material performance at 60°C and dynamic 

operation, special tanks were fabricated to allow the coupons to be exposed at a constant flow rate and 

constant temperature. A schematic representation of one tank is shown in Fig. C-1. The stir tanks were 

located in an outdoor roofed facility where they were subjected to ambient temperature fluctuations. 

Therefore, it was necessary to establish a temperature control system to maintain a constant 60°C fluid 

temperature under diurnal conditions. The chambers were composed of stainless steel and had an overall 

cylindrical geometry. The inner diameter is 61 cm and the height is 63.5 cm. The wall thicknesses were 

approximately 2 cm, which would safely withstand 70 kPa (10 psi) of internal pressure associated with 

heating of the fuels. An inner liner composed of four removable sections (also constructed of stainless 

steel) was fabricated to enable rapid attachment and removal of the specimens. The specimens were 

mounted into holders that allowed quick release from the inner liners. The top lid contained a sealed 

bearing that allowed a motor-driven shaft to turn inside the fluid. To prevent leakage, a VitonTM o-ring 

was used to seal the top lid to the cylindrical base. A stir paddle was located at the end of the shaft to stir 

the test fuels. The shaft was operated using a Leeson Hydro-Tech electrical motor designed for continual 

use, and a Teco controller was used to control the rotational speed of the shaft. 
Fig. C-1. Schem

including temperatur

An outer water jacket was used to heat th

ethylene glycol and water was circulated

temperature as depicted in Fig. C-1. 

The top lid contained ports that provided

and headspace zones, enabled visual obs

out of the sealed tank during specimen re

insulated to minimize heat losses. 

Fuels. The test fuels used in this study we

is both an ASTM standard and an SAE sta

The test fuel formulation used in this stud

SAE J1681 [2]). Fuel C is composed of 50

produce swelling (in vulcanized rubber) r

gasoline [1]. The ethanol fuel blend formu

aggressive ethanol based on the formulati

CE20a. Table C-1 was extracted from Ap

aggressive ethanol used in this study to m

constituent of this formulation and is a fre

Table C

Com

Ethanol

Deionize

Sodium 

Sulfuric 

Glacial a

C-4 

ematic representation of one stir tank assembly 

ture control.

t the fluids to the operating temperature. A 50/50 mixtur

ted through a Cole Parmer Polystat recirculator to contro

ed access for pressure and temperature measurements of

bservation of the interior, and allowed for inert gas flow

 removal. Additionally, the outer surfaces of the tanks w

 were based on standard reference test fuels. The reference

 standard test fuel to be used in material compatibility exp

tudy is ASTM Reference Fuel C [1] (also designated as Fu

f 50 vol % isooctane and 50 vol % toluene and has been s

) representative of highly aromatic premium grades of au

rmulation used in this study contains 80 vol % Fuel C and

lation described in SAE J1681. The designation for this te

Appendix E of the SAE J1681 protocol and depicts the fo

 make 1 L of aggressive ethanol. Sulfuric acid is an impor

 frequent contaminant in biomass-derived ethanol. 

e C-1. Formulation to make 1.0 liter 

of aggressive ethanol 

omponent

Grams in 1.0 L of 

aggressive ethanol 

816.0 

ized water 8.103 

m chloride 0.004 

ic acid 0.021 

acetic acid 0.061 

ture of 

trol fuel 

s of the fluid 

ow into and 

s were 

nce fuel used 

experiments. 

 Fuel C by 

n shown to 

 automotive 

nd 20 vol % of 

 test fuel is 

 formulation of 

portant 
C-5 

Polymer and Metallic Coupons. Table C-2 lists the metals and elastomeric materials evaluated in this study. 

The metal-based specimens include several steels, copper, brass, and bronze. The elastomers listed are 

considered high performance elastomer products. VitonTM and DyneonTM are products of DuPont and 3M, 

respectively. Four VitonTM and four DyneonTM types were evaluated. The main difference between the types 

of fluorocarbons is the level of fluorine contained within the elastomer structure and the type of curing agent 

used to crosslink the material. The NBR used in this study is a nitrile rubber and is representative of standard 

gasoline hoses and contains no fluorine. 

Table C-2. List of metal and elastomer coupon materials 

Metal and alloy type Elastomer type 

Nickel Viton A401C 

Bronze Viton B601C 

Terne metal (lead-plated steel) Viton GF-600S 

Aluminum Viton GFLT-S 

Stainless steel Dyneon FE 5620 

Brass Dyneon FE 5840 

Mild steel Dyneon FPO 3741 

Galvanized (Zn-plated) steel Dyneon LFTE 6400 

 NBR 

The coupon geometry for the metal specimens immersed in the fluids was 2.5 cm by 5 cm and had a 

thickness of around 0.16 cm. This specimen geometry facilitates both accurate measurement of mass loss 

and subsequent surface analysis. The elastomer specimens contained several geometries that were specific 

to the type of testing being performed and were measured and tested at ambient conditions in accordance 

with ASTM D3767-03 and ASTM D471-06. Dog-bone coupons based on Die C (ASTM D412-06a test 

method A) were fabricated to obtain tensile strength, elongation at break and moduilus100. Shore A 

hardness properties were also determined on the grip portion of the dog-bone coupons prior to tensile 

testing in accordance with ASTM D2240-05. In addition, smaller rectangular specimens were evaluated 

to volume swell (ASTM D471-06). Three coupons were exposed for each material and test condition to 

obtain some measure of statistics. 

Test Protocol. The fuels were prepared by splash bending the isooctane and toluene components inside 

the stir tanks. For the CE20a fuel the aggressive ethanol component was made first and Fuel C was 

subsequently added to avoid any possible separation between the water and the Fuel C constituents. 

A table showing the test matrix is shown in Table C-3. Four batches of each specimen type were 

prepared. Each batch contained three samples for each material. However, for each metal to be tested, 

additional specimens were fabricated for installation into the headspace area to assess compatibility with 

the vapor phase only. One batch consisted of one set of the metal specimens (listed in Table C-2) and two 

sets (tensile specimens and hardness/swell specimens) of the nine elastomer types. For each material and 

coupon geometry, three specimens were evaluated for the fluid exposures. (For the headspace gas 

exposures the number of specimens per metal was two.) Therefore, the total batch size exposed to each 

fluid was 24 metal corrosion coupons and 54 elastomer coupons, of which 27 were tensile specimens and 

27 were hardness/swell specimens. 
C-6 

Table C-3. Specimen removal and insertion protocol 

Batch 

number 

Exposure protocol for specimens per batch 

Week 

introduced 

Week 

removed 

Total weeks 

exposed 

1 0 4 4 

2 0 12 12 

3 0 16 16 

4 12 16 4 

At each specimen removal interval, the elastomer specimens were placed directly from the stir tank into a 

container filled with the appropriate test fuel and allowed to cool to ambient conditions prior to testing. 

This was to ensure that the elastomer specimens remained wet in accordance with the standard test 

protocol. No such requirement was needed for the metal specimens. 

EXPERIMENTAL RESULTS 

Approximately 140 L of fuel were added to each stir tank. The vertical headspace distance (from the fuel 

level to the lid) was approximately 43 cm. The specimens were mounted inside the tank prior to adding 

the fuels. 

Stir Tank Performance. The lids were sealed and the stirrer motors were operated at 100 rpm. While the 

stirrers were running, the temperature control recirculators were set to 60°C and turned on. The motors 

and recirculators were operated continuously over each exposure period. The flow rate of the fuel past the 

specimens was estimated at 0.8m/s using a standard flow probe. The temperature of the fuel and 

headspace area was continuously monitored and showed that 8 h was required to heat the fuel from 

ambient to 60°C. Since the resulting temperature data for the two tanks were nearly identical, we have 

elected to use profile for the Fuel C tank shown in Fig. C-2 to assess the temperature performance. The 

resulting temperature profile clearly shows the three test periods. The results presented in Fig. C-2 show 

that the fluid temperature was maintained at 60°C during the 4, 12, and 16 week intervals. In contrast, the 

ambient temperature was much lower and fluctuated dramatically, reaching a low temperature of -10°C to 

a maximum approaching 25°C. The breaks in the fluid temperature are associated with the end of each 

period, at which point a portion of the specimens were removed or added per the protocol outlined in 

Table C-3. A noticeable drop in fluid temperature occurred early in the second (8 week) period between 

week 4 and week 12. This drop was caused by an unexpected power outage and was immediately 

corrected. The effect of the power outage on the overall compatibility during this timeframe is considered 

minimal. 
C-7 

Fig. C-2. Representative temperature profile of the stir tanks during th 

entire test period. The data were taken for the Fuel C tank; the CE20a results were 

nearly identical. 

The headspace temperature was also recorded for both vessels, and the average values are shown in 

Table C-4. The temperatures for the Fuel C and CE20a tanks were observed to fluctuate 5°C and 2°C over 

the course of the study, respectively. 

Table C-4. Average headspace gas temperature (°C) 

for each of the three exposure periods 

 Exposure periods 

 0–4 weeks 4–12 weeks 12–16 weeks 

Fuel C 51 46 48 

CE20a 56 54 56 

During operation the stir tanks became pressurized as the fluids were heated. The maximum pressures 

reached for the Fuel C and the CE20a fuels were 39 kPa and 67 kPa respectively. These values 

correspond closely to the theoretical value calculated for these compositions at 60°C. After reaching 

maximum value, the pressure within the CE20a stir tank was observed to drop steadily over the next 

5 weeks to a point just above ambient. This drop in pressure was caused by a leak in the bearing seal and, 

due to time constraints, was not corrected prior to the end of the 16 week exposure run. The Fuel C tank 

did not leak, and a pressure of around 35 kPa was maintained throughout the entire test period. 

Fluid (Test Fuel) Chemistry. Fluid samples were collected for the initial condition and at the end of each 

test period (4 weeks, 12 weeks, and 16 weeks). In addition, the headspace gases were collected during the 

first 4 week exposure period. The compositions of the fluid and gases were evaluated using a gas 

chromatography and mass spectrometry (GC/MS) analyzer. The compositions of the fluids and headspace 

gases are shown in Figs. C-3 and C-4 for Fuel C and CE20a, respectively. The baseline data represent the 

initial condition. For Fuel C (as shown in Fig. C-3) the headspace chemistry consisted of approximately 

70% isooctane and roughly 30% toluene. The lower vapor pressure of isooctane results in a much higher 

concentration relative to toluene in the headspace gas. The relative concentration of the two constituents 

-10

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000 2500 3000

Time, h

Temperature, o

C

Ambient Temperature

Fuel Temperature

4-weeks 12-weeks

16-weeks

-10

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000 2500 3000

Time, h

Temperature, o

C

Ambient Temperature

Fuel Temperature

4-weeks 12-weeks

16-weeks
C-8 

in the fluid is unchanged from the baseline values at the end of the 4 and 12 week periods. This test vessel 

did not leak and was therefore able to maintain fluid chemistry and volume over the entire 16 week test 

period. Note that the measured fluid chemistry at the end of 16 weeks indicated an increased 

concentration of isooctane relative to toluene. This result is likely a sampling error since there was no 

observable leak or loss of fluid in the test vessel and we would expect that the higher volatility of the 

isooctane to decrease the concentration of isooctane relative to the toluene. 

Fig. C-3. Composition of Fuel C in the headspace and in the 

fluid for each exposure period. 

Fig. C-4. Composition of CE20a in the headspace and in the 

fluid for each exposure period. 

Although the tank containing the CE20a fuel had developed a slow leak during the initial 4 week 

exposure period, the fuel chemistry was relatively unaffected during this period (as shown in Fig. C-4). A 

sample of the headspace gas showed that the gas concentration consisted of 44 vol % isooctane, 36 vol % 

toluene, and around 20% ethanol. The higher fraction of isooctane in the gas phase is due to the higher 

volatility of isooctane relative to toluene. Interestingly, the ethanol concentration was not raised above the 

fluid level, and this effect may be due to the bound water molecules present in the ethanol. At the end of 

the 12 week exposure period, the levels of isooctane and ethanol were noticeably reduced. This drop is 

likely the result of the highly volatile components escaping from the leak. The ethanol concentration had 

0

10

20

30

40

50

60

70

80

Baseline Head

Space

4-weeks 12-weeks 16-weeks

Volume Fraction, %

toluene

isooctane

0

10

20

30

40

50

60

Baseline Head

Space

4-weeks 12-weeks 16-weeks

Volume Fraction, %

toluene

isooctane

ethanol
C-9 

dropped to around 15% and the isooctane concentration was also less relative to the toluene. After 

12 weeks of exposure, the CE20a fluid had dropped around 10 cm from the original level. Approximately 

20 L of fresh CE20a was added to raise the fuel back to its original level. The addition of fresh CE20a 

raised the ethanol concentration in the vessel to around 17 vol %, which was maintained to the end of the 

final 16 week exposure period. 

Metal Coupon Results. A report detailing the metal results can be found in the ORNL/TM-2009/286 

Report entitled Preliminary Compatibility Assessment of Metallic Dispenser Materials for Service in 

Ethanol Fuel Blends by Pawel et al. The metal-based coupons were examined for discoloration and mass 

loss at the end of each exposure period. The results indicated that none of the metal coupons exposed to Fuel 

C had noticeable changes in either appearance or mass loss. There was also no significant change in mass 

loss for each metallic coupon exposed to the vapor space of either fuel type. For the 304 stainless steel, type 

1010 carbon steel, 201 nickel, and 1100 aluminum metals, there was also no change in mass and appearance 

for these materials in the CE20a fluid during the exposure periods. In contrast, the brass, bronze, terneplated steel, and galvanized steel coupons were found to exhibit a slight mass loss as shown in Table C-5. 

Table C-5. Mass loss of brass, bronze, terne-plated steel, and 

galvanized steel specimens exposed to CE20a fuel 

Batch # Exposure 

period 

Mass loss (mg) 

Brass Terne-plated 

steel 

Galvanized 

steel 

1 0–4 weeks 6.14 0.23 0.56 

2 0–12 weeks 11.05 1.26 2.08 

3 0–16 weeks 11.13 2.47 2.47 

4 12–16 weeks 2.49 3.07 5.03 

The results observed for the bronze coupons for each of the four batches were very similar to those for the 

brass specimens and, therefore, were not included into a separate column. The brass (and bronze) coupons 

were observed to exhibit the highest mass loss of the metal-based specimens. However, the corresponding 

corrosion rate for these two materials was less than 2 mils/year (which is considered low). The mass loss 

was observed to be highest during the initial 4 weeks rather than for those specimens introduced to the 

fluid and during week 12 and exposed for the final 4 week period. Interestingly, the opposite effect is 

observed for the terne-plated and galvanized steels; both of them lost a much higher mass when exposed 

to the fuel composition at the end of the test. However, taken in a larger context, these values are not 

considered significant enough to warrant concerns regarding long-term corrosion. Photographs of the 

exposed coupons are shown in Figs. C-5 and C-6 for the brass, bronze, terne-plated steel, and galvanized 

steel. The visual appearances of these specimens were essentially unaffected by exposure to the vapor 

phase of Fuel C. However, these metals exhibited discoloration when exposed to the CE20a fuels, 

indicating some degree of surface oxidation and film formation. 
C-10 

Fig. C-5. Photograph showing discoloration associated with brass and bronze specimens exposed to 

(a) Fuel C headspace, (b) between 12 and 16 weeks in CE20a, and (c) 0 to 16 weeks in CE20a. 

Fig. C-6. Photograph showing discoloration associated with terne-plated and galvanized steels exposed 

to (a) Fuel C headspace, (b) between 12 and 16 weeks in CE20a, and (c) 0 to 16 weeks in CE20a. 

Elastomer Coupon Results. The mechanical properties for the elastomers exposed to Fuel C and CE20a 

are shown in Figs. C-7 through C-12. Selected mechanical properties include the elastic modulus100

(defined as the stress at 100% elongation), tensile strength, elongation at break, and hardness. In each of 

these figures the exposure times are shown along with the initial condition and against specimens that 

were thermally aged at 60°C for 4 weeks. Since the mechanical properties of elastomers are highly 

dependent on temperature, it is important to consider property changes associated with heating to 60°C 

which are separate from the fluid effects. 

(a)

(b)

(c)

brass bronze

(a)

(b)

(c)

terne-plated steel galvanized steel
C-11 

(a) 

(b) 

Fig. C-7. Modulus of VitonTM elastomers measured for the original 

condition, thermally aged for 4 weeks at 60°C, and selected exposures at 60°C to 

(a) Fuel C and (b) CE20a. 

0

1

2

3

4

5

6

7

8

9

10

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Modulus, MPa

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S

0

1

2

3

4

5

6

7

8

9

10

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Modulus, MPa

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S
C-12 

(a) 

(b) 

Fig. C-8. Modulus100 of DyneonTM elastomers measured for the original 

condition, thermally aged for 4 weeks at 60°C, and selected exposures at 60°C to 

(a) Fuel C and (b) CE20a. 

0

1

2

3

4

5

6

7

8

9

10

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Modulus, MPa

NBR559N Dyneon FE5620

Dyneon FE5840 Dyneon FPO3741

Dyneon LTFE6400

0

1

2

3

4

5

6

7

8

9

10

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Modulus, MPa

NBR559N Dyneon FE5620

Dyneon FE5840 Dyneon FPO3741

Dyneon LTFE6400
C-13 

(a) 

(b) 

Fig. C-9. Tensile strength of NBR and Viton elastomers measured for the 

original condition, thermally aged for 4 weeks at 60°C, and selected exposures at 

60°C to (a) Fuel C and (b) CE20a. 

0

5

10

15

20

25

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Tensile strength, MPa

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S

0

5

10

15

20

25

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Tensile strength, MPa

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S
C-14 

(a) 

(b) 

Fig. C-10. Tensile strength of NBR and Dyneon elastomers measured for 

the original condition, thermally aged for 4 weeks at 60°C, and selected 

exposures at 60°C to (a) Fuel C and (b) CE20a. 

0

5

10

15

20

25

Original Aged 0-4 wks 12-16 wks 0-12 wks 0-16 wks

Tensile strength, MPa

NBR559N

Dyneon FE5620

Dyneon FE5840

Dyneon FPO3741

Dyneon LTFE6400

0

5

10

15

20

25

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Tensile strength, MPa

NBR559N

Dyneon FE5620

Dyneon FE5840

Dyneon FPO3741

Dyneon LTFE6400
C-15 

(a) 

(b) 

Fig. C-11. Shore A hardness measurements of NBR and Viton elastomers 

measured for the original condition, thermally aged for 4 weeks at 60°C, and 

selected exposures at 60°C to (a) Fuel C and (b) CE20a. 

0

20

40

60

80

100

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Hardness (Shore A)

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S

0

20

40

60

80

100

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Hardness (Shore A)

NBR559N Viton A401C

Viton B601 Viton GF-600S

Viton GFLT-S
C-16 

(a) 

(b) 

Fig. C-12. Shore A hardness measurements of NBR and DyneonTM 

elastomers measured for the original condition, thermally aged for 4 weeks at 

60°C, and selected exposures at 60°C to (a) Fuel C and (b) CE20a. 

The elastic modulus results for exposures to Fuel C and CE20a are shown in Figs. C-7 and C-8 for the 

VitonTM and DyneonTM specimens, respectively. Thermal aging (for 4 weeks) contributed to a modest 

increase in the modulus for the VitonTM and DyneonTM specimens, probably resulting from additional 

postcuring (crosslinking) of the material. In contrast, the modulus for the NBR specimens increased 20% 

during 4 weeks of thermal aging. In fact, after aging, the modulus for the NBR was higher than or equal 

to the moduli of several fluorocarbons; the exceptions were VitonTM A401C, and DyneonTM FP03741 and 

LFTE6400. All of the specimens exhibited a decrease in modulus when exposed to Fuel C. The nitrile 

rubber modulus exhibited the most dramatic drop (~50%) when exposed to Fuel C for 4 weeks and 

subsequently showed a modest increase in modulus with increased time of exposure. In contrast, the 

moduli of the elastomers remained relatively constant for each exposure period. At the end of 16 weeks in 

0

20

40

60

80

100

120

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Hardness (Shore A)

NBR559N Dyneon FE5620

Dyneon FE5840 Dyneon FPO3741

Dyneon LTFE6400

0

20

40

60

80

100

120

Original Aged 0-4 wks 12-16

wks

0-12

wks

0-16

wks

Hardness (Shore A)

NBR559N Dyneon FE5620

Dyneon FE5840 Dyneon FPO3741

Dyneon LTFE6400
C-17 

Fuel C only VitonTM A401C and DyneonTM LFTE6400 exhibited significantly higher moduli than NBR, 

with DyneonTM LFTE6400 having the best performance (in Fuel C). 

When immersed to CE20a the resulting moduli for the elastomers was lower (5 to 20%) than when 

exposed to Fuel C. The CE20a results also showed that the specimen moduli were not greatly affected by 

length of exposure time (similar to Fuel C results). However, exposure to CE20a reduced the NBR 

modulus by approximately 50-60% relative to the original baseline condition. In addition, all of the 

fluorocarbon moduli were observed to exceed the NBR results. DyneonTM LFTE6400 and VitonTM 

A401C produced the highest moduli over the entire test period. Because modulus is a measure of the 

stiffness of a material, it is an important property reflecting the resilience and elasticity of an elastomer. 

Elastomers with too low a modulus are more easily deformed, which can result in leakages. 

The tensile strength results for the VitonTM and DyneonTM specimens are shown in Figs. C-9 and C-10. 

Thermal aging was found to have minimal effect on the tensile strengths of the elastomer specimens, 

although some samples showed slight increases in strength. Exposures to Fuel C and CE20a dropped the 

tensile strengths of the VitonTM specimens to around 20–40% and 25–45%, respectively. The DyneonTM 

elastomers tensile strengths also dropped similarly. For each specimen (including the standard nitrile 

rubber sample) the length of exposure time did not have a significant effect on the tensile strength. Note 

that the Viton GFLT-S specimen exposed to Fuel C showed an average decrease from week 12 to week 

16 of exposure but, when taken in context of the large error range, is consistent with the other exposure 

results. As shown in Figs. C-9 and C-10, Viton GF-600S and Dyneon FPO3741 both exhibited 

substantially higher strengths than the other elastomer types exposed to CE20a, while the remaining 

elastomers showed only marginally higher tensile strengths than the standard NBR. 

Shore A hardness measurements were taken at five locations for each individual specimen and averaged 

together with the three coupons representing each material type. The results are shown in Figs. C-11 and 

C-12 for the VitonTM and DyneonTM samples, respectively. The hardness values dropped roughly 5-10 

points with exposure to Fuel C and 8-12 points when exposed to CE20a. The NBR hardness values 

declined 13-18 points when exposed to Fuel C versus 26-29 points for exposure to CE20a. The hardness 

results were not greatly influenced by the length of exposure in either fuel type, and the elastomers all 

performed about the same. Both fluoroelastomer products (VitonTM and DyneonTM) exhibited hardness 

increases of at least 13 points compared to NBR when exposed to CE20a. 

The degree of volume increase was measured for each elastomer specimen and is expressed as a 

percentage increase from the original volume in Fig. C-13 for both Fuel C and CE20a exposures. As seen 

in the figure, the length of exposure time did not significantly affect the volume increase for each sample. 

NBR exhibited the highest degree of volume swell of the samples tested. All of the specimen volumes did 

not exceed 20% when exposed to Fuel C, which is representative of standard grade gasoline. More 

swelling was observed for the specimens when exposed to the more aggressive solution, CE20a. The 

NBR, VitonTM AC401, and DyneonTM FE5620 exceeded 20% volume swell, and VitonTM B601 closely 

approached this value. The lowest volume swell values (<10%) were observed for DyneonTM LFTE6400 

and FE5840 along with VitonTM GF-600S. 
C-18 

(a) 

(b) 

Fig. C-13. Volume increase of elastomer specimens measured for the 

original condition, thermally aged for 4 weeks at 60°C, and selected exposures at 

60°C to (a) Fuel C and (b) CE20a. 

It is difficult to predict how the elastomers will perform as actual fuel dispenser o-rings and gaskets for a 

blended fuel consisting of 20 vol % ethanol. CE20a is not a commercial fuel formulation and was 

developed solely to make compatibility assessment in a relatively short timeframe. The combination of 

moving fluid, elevated temperature, and aggressive composition serve to accelerate compatibility 

assessments and provide a guideline for material selection based on performance. 

All of the fluorocarbons had similar hardness values and all were higher than NBR. The specimens that 

exhibited the best combination of mechanical properties and decreased swell in CE20a are DyneonTM 

LFTE6400 and VitonTM GF-600S. Interestingly, DyneonTM LFTE6400 has the highest modulus of the 

0

5

10

15

20

25

NBR559N

Viton A401C

Viton B601

Viton GF-600S

Viton GFLT-S

Dyneon FE5620Dyneon FE5840

Dyneon FPO3741

Dyneon LTFE6400

Volume swell, %

0-4 wks 12-16 wks 0-12 wks 0-16 wks

0

5

10

15

20

25

30

35

40

NBR559N

Viton A401C

Viton B601

Viton GF-600S

Viton GFLT-S

Dyneon FE5620Dyneon FE5840

Dyneon FPO3741

Dyneon LTFE6400

Volume swell, %

0-4 wks 12-16 wks 0-12 wks 0-16 wks
C-19 

specimens, while VitonTM GF-600S had the highest tensile strengths. Based on the available information, 

both of these elastomer types would offer the best compatibility matchups with an E20-type fuel. 

Interestingly, the time of exposure had a minimal effect on the mechanical properties or swell associated 

with the elastomers. Meaningful results were obtained from the initial 4 week exposure period, which 

indicates that future tests of this type do not need to be extended past this period. 

CONCLUSION 

Two specialized stir tanks were fabricated to enable a dynamic fluid environment under constant elevated 

temperature. The tank containing Fuel C maintained temperature and pressure over the study period, but 

the CE20a tank developed a small leak that caused a small change in fluid composition toward the end of 

the test. Comparison of the mechanical and physical properties of the elastomers suggests that this change 

in fuel composition had little effect on their performance. 

In general, degradation of mechanical and physical properties of the metal and elastomer specimens 

occurred during the initial 4 week exposure. Additional exposure did not noticeably enhance property 

degradation. 

Fuel C and the headspace gases did not affect the metal specimens. However, discoloration and mass loss 

was measured for the brass, bronze, terne-plated steel, and galvanized steel specimens exposed to CE20a. 

The highest mass losses were measured for the brass and bronze specimens. 

The elastomer specimens each suffered property degradation when exposed to both Fuel C and CE20a at 

60°C and flowing liquid. However, the decrease in tensile properties and hardness was higher for the 

specimens subjected to CE20a. In addition, the volume swell was also higher for the CE20a exposures. 

Interestingly, the modulus for the NBR sample actually improved with the length of exposure to Fuel C 

so that at the end of the 16 week period, the modulus for the NBR sample was comparable to the moduli 

of the elastomer samples. 

When exposed to CE20a, the elastomer specimens all had higher modulus properties and hardness values 

than the standard NBR. VitonTM A401C and DyneonTM LFTE6400 had significantly higher moduli than 

the other specimens, while VitonTM GF-600S and DyneonTM FPO 3741 produced the highest tensile 

strengths when exposed to the aggressive E20 formulation, CE20a. All the elastomer specimens 

exhibited similar hardness values when exposed to Fuel C and CE20a, and their hardness results were 

about 20% higher than the NBR sample when exposed to CE20a. The specimens that exhibited the best 

combination of mechanical/physical properties and low swelling were DyneonTM LFTE6400 and VitonTM 

GF-600S. 

The results showed that the stir tank approach can successfully evaluate the compatibility of material 

coupons to a specified test fluid. The temperature and flow rate was held constant over the test periods 

and degradation of the specimens correlated with the fluid chemistry measured in the prototype 

experiments using E25a described in Appendix A. 

ACKNOWLEDGMENTS 

The authors gratefully acknowledge the support of Dennis Smith, Director of the DOE National Clean 

Cities Program & Vehicle Technology Deployment. Oak Ridge National Laboratory is a multiprogram 

laboratory operated by UT-Battelle for the U.S. Department of Energy under contract 

DE-AC0500OR22725. We also would like to acknowledge Eric Nafziger and Norberto Domingo 

(ORNL) for their support in setting up the stir tanks.

APPENDIX D 

TABULATED DMA RESULTS 

D-3 

Table D-1. DMA results for elastomer specimens 

Storage Modulus Loss Modulus Tan Delta

Environment Elastomer Fuel Type Temp/oC Mpa Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC

Viton A401C Baseline -2.62 2812 -0.10 9.45

Fluid Viton A401C Ref C -11.05 3654 -8.18 4.72

Fluid Viton A401C CE10A -9.44 2684 -7.22 4.33

Fluid Viton A401C CE17A -12.35 2985 -10.04 2.57

Fluid Viton A401C CE25A -9.04 2794 -6.17 4.69

Vapor Viton A401C Ref C -6.65 3220 -4.55 5.89

Vapor Viton A401C CE10A -9.94 3265 -6.90 5.32

Vapor Viton A401C CE17A -9.86 3673 -7.14 5.25

Vapor Viton A401C CE25A -7.90 3355 -5.28 6.33

Viton B601C Baseline 0.21 2445 2.30 9.64

Fluid Viton B601C Ref C -6.64 2436 -4.51 5.66

Fluid Viton B601C CE10A -6.64 2548 -4.84 5.57

Fluid Viton B601C CE17A -10.52 2918 -8.10 4.14

Fluid Viton B601C CE25A -6.77 3119 -4.12 5.54

Vapor Viton B601C Ref C -3.74 2413 -1.38 8.42

Vapor Viton B601C CE10A -6.21 3170 -3.62 6.05

Vapor Viton B601C CE17A -7.31 3170 -5.02 6.01

Vapor Viton B601C CE25A -4.36 3086 -2.08 7.17

Viton GF-600S Baseline 8.31 2235 10.41 17.34

Fluid Viton GF-600S Ref C -0.46 2314 1.09 13.38

Fluid Viton GF-600S CE10A 0.24 2308 1.54 13.04

Fluid Viton GF-600S CE17A -2.08 2159 -0.79 11.36

Fluid Viton GF-600S CE25A 0.22 2425 2.63 13.11

Vapor Viton GF-600S Ref C 3.06 2123 4.97 14.72

Vapor Viton GF-600S CE10A 0.45 2618 2.65 13.07

Vapor Viton GF-600S CE17A 0.50 2588 2.57 13.25

Vapor Viton GF-600S CE25A 2.42 2470 4.30 13.82

Viton GFLT-600S Baseline -11.17 2150 -9.10 -1.85

Fluid Viton GFLT-600S Ref C -12.59 2158 -11.78 -3.33

Fluid Viton GFLT-600S CE10A -12.97 2275 -11.75 -4.21

Fluid Viton GFLT-600S CE17A -15.31 2000 -13.34 -4.71

Fluid Viton GFLT-600S CE25A -13.58 2256 -11.17 -3.09

Vapor Viton GFLT-600S Ref C -12.95 2682 -10.80 -1.67

Vapor Viton GFLT-600S CE10A -14.15 2875 -11.99 -3.87

Vapor Viton GFLT-600S CE17A -13.03 2783 -11.76 -3.61

Vapor Viton GFLT-600S CE25A -12.01 2588 -10.45 -2.88

Dyneon FE5620 Baseline -3.39 3105 -1.00 7.75

Fluid Dyneon FE5620 Ref C -10.31 3080 -8.06 3.26

Fluid Dyneon FE5620 CE10A -11.39 3196 -8.46 3.48

Fluid Dyneon FE5620 CE17A -12.80 2717 -10.18 2.01

Fluid Dyneon FE5620 CE25A -9.90 2917 -7.09 3.67

Vapor Dyneon FE5620 Ref C -8.07 3343 -5.49 4.72

Vapor Dyneon FE5620 CE10A -9.36 3416 -7.49 3.58

Vapor Dyneon FE5620 CE17A -11.56 3715 -8.74 2.76

Vapor Dyneon FE5620 CE25A -8.85 3066 -6.18 3.60

Dyneon FE5840 Baseline 7.41 2437 9.74 15.36

Fluid Dyneon FE5840 Ref C -0.14 2573 1.85 11.46

Fluid Dyneon FE5840 CE10A -2.27 2635 0.61 12.27

Fluid Dyneon FE5840 CE17A -3.90 2320 -0.98 10.57

Fluid Dyneon FE5840 CE25A -0.44 2580 2.25 12.35

Vapor Dyneon FE5840 Ref C 3.33 2691 5.87 13.14

Vapor Dyneon FE5840 CE10A 0.35 2821 3.03 11.90

Vapor Dyneon FE5840 CE17A 0.03 2925 1.98 12.46

Vapor Dyneon FE5840 CE25A 1.76 2690 4.46 12.64

Dyneon FPO3741 Baseline 5.51 2092 7.99 15.54

Fluid Dyneon FPO3741 Ref C -3.31 2528 -1.82 10.92

Fluid Dyneon FPO3741 CE10A -2.78 1979 -1.53 10.54

Fluid Dyneon FPO3741 CE17A -8.02 2802 -5.07 10.09

Fluid Dyneon FPO3741 CE25A -3.26 2390 -1.34 11.23

Vapor Dyneon FPO3741 Ref C 0.66 2462 3.15 12.77

Vapor Dyneon FPO3741 CE10A -0.92 2218 -0.19 11.13

Vapor Dyneon FPO3741 CE17A -3.85 2957 -2.15 11.68

Vapor Dyneon FPO3741 CE25A -1.18 2191 0.52 11.25

Dyneon LTFE6400 Baseline -26.33 3701 -24.33 -16.96

Fluid LTFE6400 Ref C -25.88 2837 -23.89 -16.88

Fluid LTFE6400 CE10A -26.05 3044 -24.19 -17.19

Fluid LTFE6400 CE17A -27.40 3256 -25.61 -18.53

Fluid LTFE6400 CE25A -25.79 2943 -23.65 -17.48

Vapor LTFE6400 Ref C -27.47 4482 -24.23 -17.12

Vapor LTFE6400 CE10A -26.01 3208 -24.23 -17.19

Vapor LTFE6400 CE17A -26.84 3455 -24.71 -17.68

Vapor LTFE6400 CE25A -27.28 3271 -25.08 -17.66
D-4 

Table D-2. DMA results for NBR specimens 

Environment Elastomer Fuel Type Temp/oC Mpa Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC

NBR #1 Baseline -18.01 4537 -14.12 -4.26

Fluid NBR #1 Ref C -7.24 6153 0.41 7.59

Fluid NBR #1 CE10A -11.48 6776 -2.29 5.74

Fluid NBR #1 CE17A -12.90 6655 -5.26 4.32

Fluid NBR #1 CE25A -10.02 5851 -1.83 6.24

Vapor NBR #1 Ref C -13.43 5280 -7.87 0.10

Vapor NBR #1 CE10A -7.87 7488 -0.54 6.78

Vapor NBR #1 CE17A -10.90 6344 -3.12 4.16

Vapor NBR #1 CE25A -10.80 6332 -5.27 2.21

NBR #2 Baseline -25.02 4847 -22.28 -12.28

Fluid NBR #2 Ref C -7.95 5988 -2.20 5.64

Fluid NBR #2 CE10A -11.98 6180 -6.10 1.50

Fluid NBR #2 CE17A -14.20 5970 -8.35 0.55

Fluid NBR #2 CE25A -9.38 6249 -3.67 4.24

Vapor NBR #2 Ref C -15.24 5866 -10.64 -1.83

Vapor NBR #2 CE10A -7.81 6755 -1.83 6.06

Vapor NBR #2 CE17A -11.89 5626 -5.89 1.94

Vapor NBR #2 CE25A -12.16 6199 -8.25 0.07

NBR #3 Baseline -9.49 4532 -7.76 -0.23

Fluid NBR #3 Ref C -2.64 4362 -0.46 7.15

Fluid NBR #3 CE10A -10.49 4239 -6.18 -2.39 34.75

Fluid NBR #3 CE17A -6.92 3734 -5.19 5.34

Fluid NBR #3 CE25A -7.23 4821 -2.83 17.37

Vapor NBR #3 Ref C -7.39 3927 -5.51 1.65

Vapor NBR #3 CE10A -3.27 4819 -1.31 6.43

Vapor NBR #3 CE17A -4.87 4758 -2.32 5.70

Vapor NBR #3 CE25A -8.16 4212 0.89 -5.77

NBR #4 Baseline -34.94 2914 -26.69 -2.15 -23.15 4.60

Fluid NBR #4 Ref C -20.98 4962 -15.64 5.44 -12.66 10.52

Fluid NBR #4 CE10A -23.35 5622 -17.11 3.62 -13.44 9.42

Fluid NBR #4 CE17A -29.98 4534 -21.63 1.24 -17.48 7.87

Fluid NBR #4 CE25A -21.48 5009 -16.07 5.00 -12.15 10.22

Vapor NBR #4 Ref C -28.94 4239 -22.80 -0.74 -19.43 5.86

Vapor NBR #4 CE10A -22.17 5176 -16.61 2.81 -13.86 8.60

Vapor NBR #4 CE17A -27.34 4908 -22.36 -0.67 -18.66 5.67

Vapor NBR #4 CE25A -26.03 3955 -20.17 0.48 -17.36 5.72

NBR #5 Baseline -27.29 4779 -21.81 -2.92

Fluid NBR #5 Ref C -8.37 5397 -2.71 8.16

Fluid NBR #5 CE10A -15.17 4386 -9.93 4.59

Fluid NBR #5 CE17A -12.91 5558 -8.85 4.94

Fluid NBR #5 CE25A -9.19 5912 -6.10 8.31

Vapor NBR #5 Ref C -16.91 4998 -13.64 1.94

Vapor NBR #5 CE10A -6.41 6415 -2.03 8.50

Vapor NBR #5 CE17A -11.32 5092 -5.69 6.73

Vapor NBR #5 CE25A -15.19 5542 -10.58 3.35

NBR #6 Baseline -25.01 5062 -22.22 -15.21

Fluid NBR #6 Ref C -10.50 4313 -5.38 -1.57

Fluid NBR #6 CE10A -17.51 5883 -12.58 -9.59

Fluid NBR #6 CE17A -15.45 4947 -10.43 -5.60

Fluid NBR #6 CE25A -12.66 5990 -6.84 -1.23

Vapor NBR #6 Ref C -19.10 5537 -15.17 -9.81

Vapor NBR #6 CE10A -13.36 6600 -8.74 -3.88

Vapor NBR #6 CE17A -11.44 4540 -7.72 -3.37

Vapor NBR #6 CE25A -16.24 5857 -12.04 -7.36

Storage Modulus Loss Modulus Tan Delta
D-5 

Table D-3. DMA results for non-fluorocarbons and non-NBRs 

Environment Elastomer Fuel Type Temp/oC Mpa Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC Temp/oC

Fluorosilicone LM15 Baseline -53.72 3229 -121.81 -49.79 -119.97 -43.94

Fluid uorosilicone LM15 Ref C -53.76 3538 -50.01 -44.55

Fluid uorosilicone LM15 CE10A -53.67 3509 -49.74 -44.40

Fluid uorosilicone LM15 CE17A -51.68 2910 -49.01 -44.24

Fluid uorosilicone LM15 CE25A -51.92 3204 -48.58 -44.33

Vapor uorosilicone LM15 Ref C -53.30 3920 -50.49 -44.74

Vapor uorosilicone LM15 CE10A -52.79 3699 -49.85 -44.46

Vapor uorosilicone LM15 CE17A -52.33 3710 -49.45 -44.45

Vapor uorosilicone LM15 CE25A -53.25 4097 -50.21 -44.78

Polyurethane Baseline -15.93 2493 -12.95 -4.67

Fluid Polyurethane Ref C -16.61 2545 -13.32 -4.52

Fluid Polyurethane CE10A -19.38 2841 -16.91 -6.05

Fluid Polyurethane CE17A -18.15 2693 -15.93 -4.82

Fluid Polyurethane CE25A -17.54 2768 -15.36 -4.90

Vapor Polyurethane Ref C -17.28 2911 -14.76 -6.49

Vapor Polyurethane CE10A -17.08 2827 -15.23 -5.15

Vapor Polyurethane CE17A -16.18 2731 -14.60 -4.83

Vapor Polyurethane CE25A -18.68 2791 -16.13 -6.34

Neoprene Rubber Baseline -98.23 4782 -92.32 -22.66 -87.85 -13.23

Fluid Neoprene Rubber Ref C -101.84 5840 -93.15 -12.30 -91.05 -5.59

Fluid Neoprene Rubber CE10A -100.95 6740 -92.83 -12.12 -91.63 -5.69

Fluid Neoprene Rubber CE17A -100.47 5728 -93.06 -12.04 -90.60 -4.72

Fluid Neoprene Rubber CE25A -102.25 6295 -93.79 -12.48 -91.90 -6.34

Vapor Neoprene Rubber Ref C -98.32 5989 -91.94 -34.31 -18.63 -91.94 -8.57

Vapor Neoprene Rubber CE10A -100.30 6426 -93.27 -18.17 -90.57 -9.41

Vapor Neoprene Rubber CE17A -100.98 5960 -91.62 -12.60 -91.62 -5.50

Vapor Neoprene Rubber CE25A -102.46 6901 -93.62 -13.10 -92.58 -6.66

Styrene Butadiene Rub Baseline -37.47 4018 -32.24 -2.15 -29.85 2.05 67.14

Fluid ene Butadiene Rub Ref C -32.63 4422 -27.73 -2.62 -25.81 1.27 80.21

Fluid ene Butadiene Rub CE10A -33.67 4718 -28.62 -3.19 -27.06 0.00 78.44

Fluid ene Butadiene Rub CE17A -34.93 4615 -29.84 -3.68 -27.35 1.01 77.95

Fluid ene Butadiene Rub CE25A -33.19 4291 -27.73 -1.80 -25.98 1.44 79.47

Vapor ene Butadiene Rub Ref C -35.86 4543 -30.09 -1.83 -26.72 2.55 67.47

Vapor ene Butadiene Rub CE10A -32.39 5275 -28.26 -2.79 -25.93 1.37 79.21

Vapor ene Butadiene Rub CE17A -33.61 5239 -28.68 -2.59 -26.66 1.77 75.61

Vapor ene Butadiene Rub CE25A -35.67 4256 -30.76 -2.61 -27.90 2.58 71.27

Silicone Rubber S060 Baseline -117.55 7585 -111.31 -107.39 -27.42 51.28

Fluid icone Rubber S060 Ref C -118.99 6848 -111.36 -106.76 -26.96

Fluid icone Rubber S060 CE10A -118.58 8101 -111.64 -108.29 -26.31

Fluid icone Rubber S060 CE17A -118.19 5665 -111.59 -106.99 -25.38

Fluid icone Rubber S060 CE25A -118.07 7715 -111.91 -107.91 -27.77

Vapor icone Rubber S060 Ref C -117.23 7342 -111.09 -107.24 -27.31

Vapor icone Rubber S060 CE10A -118.23 7704 -112.06 -107.06 -25.59

Vapor icone Rubber S060 CE17A -117.76 6210 -111.56 -107.77 -26.10

Vapor icone Rubber S060 CE25A -117.82 7323 -111.21 -107.48 -27.16

Storage Modulus Loss Modulus Tan Delta