Test - 45654414 - Rubber

DOT HS 811 296 March 2010
NHTSA Tire Aging Test

Development Project -
Tire Innerliner Analysis
DISCLAIMER
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Highway Traffic Safety Administration in the interest of information exchange.
The opinions, findings, and conclusions expressed in this publication are those of
the authors and not necessarily those of the Department of Transportation or the
National Highway Traffic Safety Administration. The United States Government
assumes no liability for its contents or use thereof. If trade names, manufacturers’
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TECHNICAL REPORT DOCUMENTATION PAGE
1. Report No. 2. Government Accession No. 3. Recipient's Catalog No.
DOT HS 811 296
4. Title and Subtitle 5. Report Date
NHTSA Tire Aging Test Development Project - March 2010
Tire Innerliner Analysis 6. Performing Organization Code
7. Author(s) 8. Performing Organization Report No.

Uday Karmarkar1, Ana Barbur1, Edward R. Terrill, Ph.D.1, Mark Centea1, Larry
R. Evans2, James D. MacIsaac Jr.3
1
Akron Rubber Development Laboratory, Inc., 2Transportation Research Center
Inc., 3National Highway Traffic Safety Administration
9. Performing Organization Name and Address 10. Work Unit No. (TRAIS)
Akron Rubber Development Laboratory, Inc.
2887 Gilchrist Rd. 11. Contract or Grant No.
Akron, Ohio 44305 DTNH22-03-D-08660,

DTNH22-07-D-00060
12. Sponsoring Agency Name and Address 13. Type of Report and Period Covered
National Highway Traffic Safety Administration Final
1200 New Jersey Avenue SE. 14. Sponsoring Agency Code
Washington, D.C. 20590

15. Supplementary Notes
Project support, testing, and analysis services provided by the Akron Rubber Development Laboratory, Smithers
Scientific Services, Inc., Standards Test Labs, and Transportation Research Center, Inc.
16. Abstract
As a result of the TREAD Act of 2000, NHTSA initiated an effort to develop a laboratory-based accelerated service
life test for light vehicle tires (herein referred to as a “tire aging test”). Scientific literature attributes the changes in
properties of the tire rubber compounds and their interfaces to thermal-oxidation, a chemical reaction that involves
heat and oxygen. Since the innerliner is the main barrier to permeation of the pressurized inflation gas (air containing
degradative oxygen) through the tire, it was desired to know material composition, thickness, and permeability of a
large cross-section of passenger vehicle tire innerliners in order to understand their influence on whole-tire
performance in a tire aging test. Though example formulations for tire innerliner compounds are common in
literature, the actual composition of a given tire’s innerliner is not publicly available. Currently there is no published
analytical method for determining the exact material composition of the innerliner, which led to the development of
the methodology outlined in this paper.
Once an optimal innerliner analysis methodology was determined, the innerliners of six tire models collected from
on-vehicle service in Phoenix, AZ, and 37 additional models used in laboratory phases of the project were analyzed.
Microscopy analysis was used to determine innerliner gauge and placement. Innerliner permeability at two
temperatures was measured on extracted innerliner slices. The air permeability results were correlated with the
innerliner compositional results. Also completed were indentation modulus profiles of the innerliners of tires
retrieved from service and after accelerated laboratory aging, which were benchmarked against new tires of each
model. Results showed changes in the innerliner as a function of age (for in-service tires), as well as during
accelerated laboratory aging tests. It is hypothesized that the observed changes in innerliner modulus during service
or accelerated aging may affect the liner’s permeability and/or flexibility over time.
17. Key Words 18. Distribution Statement
Tire, aging, innerliner, butyl, polymer, permeability, tire Document is available to the public from the
safety, Phoenix, spare tire, accelerated service life National Technical Information Service
www.ntis.gov
19. Security Classif. (of this report) 20. Security Classif. (of this page) 21. No. of Pages 22. Price
Unclassified Unclassified 104
Form DOT F 1700.7 (8-72) Reproduction of completed page authorized
i
TABLE OF CONTENTS
EXECUTIVE SUMMARY .......................................................................................................... vii
BACKGROUND ............................................................................................................................ 1
TEST TIRES ................................................................................................................................... 2
In-Service (Field) Tires ............................................................................................................... 2
Oven Aged Tires ......................................................................................................................... 2
Wheel-Tested (LTDE and P-END) Tires ................................................................................... 2
EXPERIMENTAL TECHNIQUES ................................................................................................ 2
Fourier Transform Infrared Spectroscopy (FTIR) ...................................................................... 3
Beilstein ...................................................................................................................................... 3
Energy Dispersive X-ray Spectroscopy (EDAX) ....................................................................... 3
X-ray Fluorescence (XRF) .......................................................................................................... 4
Pyrolysis-Gas Chromatography/Flame Ionization Detector (GC/FID) ...................................... 5
Pyrolysis-Gas Chromatography/Mass Spectroscopy (GC/MS) .................................................. 5
Thermal Gravimetric Analysis (TGA) ........................................................................................ 6
Extraction .................................................................................................................................... 6
Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-AES) ................................. 7
Oxygen Content (Fixed Oxygen by Weight) .............................................................................. 8
Permeability ................................................................................................................................ 8
Microscopy ................................................................................................................................. 9
Indentation Modulus ................................................................................................................... 9
ASTM D 2240 Type A Durometer Hardness ........................................................................... 10
INNERLINER FORMULA RECONSTRUCTION ..................................................................... 11
REGRESSION ANALYSIS ......................................................................................................... 13
RESULTS ..................................................................................................................................... 13
Part I - Model Liner Compound Chemical Analysis ................................................................ 13
Part II - Chemical Analysis of the Innerliner from Six Tire Models Retrieved from Service in
Phoenix, AZ .............................................................................................................................. 26
Part II - Chemical Analysis of the Innerliners from Addition Tire Models.............................. 29
Part IV - Permeability of Model Compounds ........................................................................... 48
Part V - Permeability of Innerliners from Production Tires ..................................................... 54
Part VI - Microscopy of Innerliners from Production Tires ..................................................... 60
Part VII - Indentation Modulus of Innerliners from Production Tires...................................... 62
CONCLUSIONS........................................................................................................................... 84
REFERENCES ............................................................................................................................. 91
ii
LIST OF FIGURES
Figure 1. FTIR Test......................................................................................................................... 3
Figure 2. SEM/EDAX Test ............................................................................................................. 4
Figure 3. XRF Test ......................................................................................................................... 5
Figure 4. Pyrolysis GC/FID Test .................................................................................................... 5
Figure 5. TGA Test ......................................................................................................................... 6
Figure 6. Extraction Test................................................................................................................. 7
Figure 7. ICP-AES Test .................................................................................................................. 8
Figure 8. Permeability Test ............................................................................................................. 9
Figure 9. Microscopy ...................................................................................................................... 9
Figure 10. Modulus Profiling Test ................................................................................................ 10
Figure 11. Overlay Plot of the TGA Weight Loss Curves ........................................................... 19
Figure 12. Overlay Plot of the TGA Derivative Curves .............................................................. 19
Figure 13. TGA Derivative Curves for Model Compounds 1, 18, 2, 3, 4, 5, and 6. .................... 20
Figure 14. TGA Derivative Curves for Model Compounds 7, 8, 9, 10: Increasing Levels of
Natural Rubber with Chlorobutyl ................................................................................................. 21
Figure 15. TGA Derivative Curves for Model Compounds 1, 13, 14, 15, 16, 17: Increasing
Levels of oil-extended SBR with Bromobutyl.............................................................................. 21
Figure 16. TGA Derivative Curves for Model Compounds 1, 7, 11: ........................................... 22
Figure 17. FTIR of Model Liner Compounds 1, 3, 5, 7, 9............................................................ 23
Figure 18. Correlation between XRF Bromine Content and phr Bromobutyl.............................. 24
Figure 19. Correlation between XRF Chlorine Content and phr Chlorobutyl.............................. 25
Figure 20. Correlation between Bromine Intensity and phr Bromobutyl ..................................... 26
Figure 21. Correlation between Chlorine Intensity and phr Chlorobutyl ..................................... 26
Figure 22. Pyrolysis-GC/FID Analysis of SBR (1502) Gum Polymer ......................................... 38
Figure 23. Pyrolysis-GC/FID Analysis of BIIR Gum Polymer .................................................... 38
Figure 24. Pyrolysis-GC/FID Analysis of Natural Rubber Gum Polymer ................................... 39
Figure 25. Pyrolysis-GC/FID Calibration Curve for Polyisobutylene Based on Isobutylene ...... 39
Figure 26. Pyrolysis-GC/FID Calibration Curve for Polyisoprene Based on Isoprene ................ 40
Figure 27. Pyrolysis-GC/FID Calibration Curve for Styrene Butadiene Polymer Based on
Styrene .......................................................................................................................................... 40
Figure 28. Pyrolysis-GC/FID Calibration Curve for Styrene Butadiene Polymer Based on
Butadiene ...................................................................................................................................... 41
Figure 29. Pyrolysis-GC/MS Calibration Curve for Polyisobutylene Based on Isobutylene ....... 43
Figure 30. Pyrolysis-GC/MS Calibration Curve for Polyisobutylene Based on Isobutylene
Tetramer ........................................................................................................................................ 44
Figure 31. Pyrolysis-GC/MS Calibration Curve for Polyisoprene Based on Isoprene................. 44
Figure 32. Pyrolysis-GC/MS Calibration Curve for Polyisoprene Based on Isoprene Dimer ..... 45
Figure 33. Pyrolysis-GC/MS Calibration Curve for Styrene Butadiene Polymer Based on Styrene
....................................................................................................................................................... 45
Figure 34. Pyrolysis-GC/MS Calibration Curve for Styrene Butadiene Polymer Based on
Butadiene Dimer ........................................................................................................................... 46
Figure 35. Permeability of Model Compounds at 21°C as a Function of Butyl Content ............. 51
iii
Figure 39. Permeability of Tire Innerliners at 21°C as a Function of Butyl Content ................... 57
Figure 40. Permeability of Tire Innerliners at 65°C as a Function of Butyl Content ................... 59
Figure 41. Microscopy Innerliner Analysis of Production Tires .................................................. 62
Figure 42. Indentation Modulus Test Samples and Plots for a Phoenix-Retrieved Tire .............. 63
Figure 43. Average Indentation Modulus of Shoulder Region Innerliner as a Function of Age .. 64
Figure 44. Average Change in Indentation Modulus of Shoulder Region Innerliner for Six Tire
Models During Service in Phoenix, AZ........................................................................................ 65
Figure 45. Average Change in Indentation Modulus of the Shoulder Region Innerliner Versus
LTDE Roadwheel Hours............................................................................................................... 67
Figure 46. Average Change in Indentation Modulus of the Shoulder Region Innerliner Versus P-
END Roadwheel Hours................................................................................................................. 68
Figure 47. Average Change in Indentation Modulus of Shoulder Region Innerliner for Capped-
Inflation Oven Aging .................................................................................................................... 70
Figure 48. Model Prediction of Innerliner Indentation Modulus with Capped-Inflation Oven
Aging............................................................................................................................................. 71
Figure 49. Change in Average Indentation Modulus of Innerliner in Shoulder Region for 8
Weeks Oven Aging @ 65°C with 23-hour Break-in .................................................................... 74
Figure 50. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 3 or 5
Weeks Oven Aging @ 65°C with 2-hour Break-in ...................................................................... 76
Figure 51. Average Indentation Modulus of Innermost Layer of Bead Region for Five Phoenix
Tire Models ................................................................................................................................... 78
Figure 52. Average Indentation Modulus of Innermost Layer in Bead Region for Capped-
Inflation Oven Aging .................................................................................................................... 79
Figure 53. Change in Average Indentation Modulus of Innerliner in Bead Region for 8 Weeks
Oven Aging @ 65°C with 23-hour Break-in ................................................................................ 80
Figure 54. Change in Average Indentation Modulus of Innerliner in Bead Region for 3 or 5
Weeks Oven Aging @ 65°C with 2-hour Break-in (at 50 mph)................................................... 82
iv
LIST OF TABLES
Table 1. Model Innerliner Formulation ........................................................................................ 12
Table 2. Analyses Used in Formula Reconstruction Estimates for Innerliner Compounds ......... 12
Table 3. Model Bromobutyl/Natural Rubber Liner Compounds .................................................. 14
Table 4. Model Chlorobutyl/Natural Rubber Liner Compounds .................................................. 15
Table 5. Model Bromobutyl/SBR Liner Compounds ................................................................... 16
Table 6. Six Additional Model Compounds for Liner Permeability Testing ............................... 16
Table 7. Acetone Extraction of Model Liner Compounds ............................................................ 17
Table 8. Oxygen Content of Model Liner Compounds ................................................................ 17
Table 9. Ash Composition of Model Liner Compounds............................................................... 18
Table 10. TGA Compositional Analysis (wt%)............................................................................ 20
Table 11. Actual Compositional Analysis (wt%) ......................................................................... 20
Table 12. FTIR Analysis ............................................................................................................... 22
Table 13. XRF Analysis Results of Model Compounds ............................................................... 24
Table 14. EDAX of Model Compounds ....................................................................................... 25
Table 15. List of Six Phoenix-Retrieved Tire Models .................................................................. 27
Table 16. Acetone Extractables (wt%) of the Six Phoenix Tire Models ...................................... 27
Table 17. ICP-AES Analysis of the Six Phoenix Tire Models ..................................................... 27
Table 18. TGA Compositional Analysis of the Six Phoenix Tire Models (wt%) ........................ 28
Table 19. Beilstein and FTIR Results ........................................................................................... 28
Table 20. XRF Analysis Results ................................................................................................... 28
Table 21. EDAX Results for Chlorine and Bromine Analysis ..................................................... 29
Table 22. EDAX Prediction for Chlorobutyl and Bromobutyl ..................................................... 29
Table 23. EDAX Results for Other Elements Analysis ................................................................ 29
Table 24. Thirty Seven Additional Production Tires Models Analyzed by Extraction, TGA, XRF,
Pyrolysis-GC/MS .......................................................................................................................... 30
Table 25. Acetone Extractables (wt%) of Additional Tires .......................................................... 31
Table 26. Composition Analysis by TGA..................................................................................... 32
Table 27. XRF Analysis of 31 Tire Innerliners ............................................................................ 35
Table 28. EDAX Results (for Bromine and Chlorine) ................................................................. 36
Table 29. EDAX Prediction of Tire Innerliner Polymers ............................................................. 36
Table 30. EDAX Results (for Other Elements) ............................................................................ 37
Table 31. Pyrolysis-GC/FID Peak Identification .......................................................................... 37
Table 32. Pyrolysis-GC/FID Analysis Summary.......................................................................... 41
Table 33. Pyrolysis-GC/MS Peak Identification .......................................................................... 43
Table 34. Pyrolysis-GC/MS Analysis Summary .......................................................................... 47
Table 35. Summary of Average GC Innerliner Composition by Tire Manufacturer.................... 48
Table 36. Conversion Table .......................................................................................................... 49
Table 37. Air Permeability Literature Values ............................................................................... 49
Table 38. Model Liner Compound Air Permeability Data ........................................................... 50
Table 39. 21°C Model Compound Permeability Data (66.4 cm2 Cell Size) ................................ 52
Table 40. 65°C Model Compound Permeability Data (66.4 cm2 Cell Size) ............................... 52
Table 41. Innerliner Permeability Data at 21°C for the Six Field Tire Models ............................ 55
Table 42. Innerliner Permeability Data at 21°C for Subsequent Test Tires ................................. 56
Table 43. Innerliner Permeability Data at 65°C for Six Field Tire Models.................................. 58
v
Table 44. Innerliner Permeability Data at 65°C for Subsequent Test Tires ................................. 58
Table 45. Microscopy Innerliner Analysis of Production Tires ................................................... 60
Table 46. Average Change in Indentation Modulus of Shoulder Region Innerliner During Service
in Phoenix, AZ .............................................................................................................................. 66
Table 47. Average Change in Indentation Modulus of the Shoulder Region Innerliner During
LTDE Testing ............................................................................................................................... 67
Table 48. Oven Aging Conditions with Capped Inflation Gas - Six Phoenix Tire Models ......... 69
Table 49. Average Change in Indentation Modulus of Shoulder Region Innerliner During
Capped-Inflation Oven Aging....................................................................................................... 70
Table 50. Regression Analysis of Innerliner Modulus as a Function of Oven Temperature and
Tire Type....................................................................................................................................... 72
Table 51. Oven Aging Conditions with Vent and Refill of Inflation Gas - 21 Additional Tire
Models........................................................................................................................................... 73
Table 52. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 8 Weeks
Oven Aging @ 65°C with 23-hour Break-in ................................................................................ 75
Table 53. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 3 or 5
Weeks Oven Aging @ 65°C with 2-hour Break-in ...................................................................... 77
Table 54. Change in Avg. Indentation Modulus of Innerliner in Bead Region During Service in
Phoenix, AZ .................................................................................................................................. 78
Table 55. Average Change in Indentation Modulus of Innermost Layer in the Bead Region
During Capped-Inflation Oven Aging .......................................................................................... 79
Table 56. Change in Average Indentation Modulus of Innerliner in Bead Region for 8 Weeks
Oven Aging @ 65°C with 23-hour Break-in (at 50 mph) ............................................................ 81
Table 57. Change in Avg. Indentation Modulus of Innerliner in Bead Region for 3 or 5 Weeks
Oven Aging @ 65°C with 2-hour Break-in .................................................................................. 83
Table 58. Summary Table of Average Change and Rate of Change in Innerliner Modulus by
Condition....................................................................................................................................... 84
vi
EXECUTIVE SUMMARY
In reviewing potential upgrades to the Federal Motor Vehicle Safety Standards (FMVSS) for
tires, the United States Department of Transportation, National Highway Traffic Safety Adminis-
tration initiated an effort to develop a laboratory-based accelerated service life test for light ve-
hicle tires (herein referred to as a “tire aging test”). Laboratory tire aging tests attempt to simu-
late, in an accelerated manner, the degradative process that tires experience while in service, and
then evaluate the durability of the tire in an “aged” state. It is believed that if such a test method
was successful, then light vehicle tires could eventually be required to meet standards that would
make them more resistant to operational degradation and possibly reduce their failure rate during
normal highway service.
Scientific literature attributes the changes in properties of the tire rubber compounds and their
interfaces to thermal-oxidation, a chemical reaction that involves heat and oxygen. A key tire
component affecting thermal-oxidation in tires is the innerliner, since it slows the diffusion of air
(more importantly oxygen in air) from the pressurized internal tire cavity through the tire struc-
ture during service. The permeation of inflation gas out of the tire also reduces inflation pressure,
which must be continually maintained by the consumer or the tire will be operated in an underin-
flated state. Operation of the tire while underinflated is known to increase rolling resistance and
wear, and with increasing amounts of underinflation can lead to thermal flex-fatigue damage or
destruction of the tire. Therefore, modern tubeless radial tires employ a low-permeability inner-
liner layer that lessens the permeation of the inflation gas through the tire. Innerliner polymer
compositions, filler levels, thicknesses, and placement techniques vary widely between manufac-
turers. The overall thickness and construction features of a tire also factor into the inflation gas
permeation rates. For instance, a thick light truck tire may have a lower inflation pressure loss
rate than a thin high performance passenger tire at the same pressure when using identical inner-
liner compounds and thicknesses. Therefore, for each tire design, the manufacturer determines a
desired balance between innerliner cost, production constraints, and performance.
Since the innerliner is the main barrier to permeation of the pressurized inflation gas (containing
degradative oxygen) through the tire, it was desired to know material composition, thickness, and
permeability of a large cross-section of passenger vehicle tire innerliners in order to understand
their influence on whole-tire performance in a tire-aging test. Though example formulations for
tire innerliner compounds are common in literature, the actual composition of a given tire’s in-
nerliner, which can vary in formulation even between tires from the same plant, is not publicly
available. The authors were unable to identify a published analytical method for determining the
exact material composition of an innerliner. Therefore, model innerliner compounds with known
formulations were used to establish analytical baselines in the development of a methodology to
determine a tire’s innerliner composition.
Once an optimal analysis methodology was determined, the innerliners of six tire models col-
lected from on-vehicle service in Phoenix, AZ, as well as 37 additional models used in laborato-
ry phases of the project were analyzed. Microscopy analysis of tire cross-sections was used to
determine innerliner gauge and placement. Innerliner permeability was measured on extracted
liner slices. The air permeability results were correlated with the innerliner compositional results,
for which butyl content was determined to be a major factor affecting permeability rates.
vii
The next topic examined was whether or not the modulus of tire innerliners changed during ser-
vice. First, results from six tire models retrieved from service in Phoenix, AZ indicated that the
innerliner in the shoulder region of the tires increased by approximately 0.21 MPa per year, and
the innermost layer of the bead region (not always innerliner) increased 0.23 MPa per year. Total
increases of 1.79 MPa in the shoulder region and 4.76 MPa in the bead region were observed
during long terms of service. The second topic compared the changes in the modulus of tire in-
nerliners during accelerated aging to the magnitudes observed in tires retrieved from on-vehicle
service. For the original six tire models collected in Phoenix, both the roadwheel and oven acce-
lerated aging tests could produce changes in innerliner modulus that were similar to those ob-
served in on-vehicle tires. The magnitude of the increase in innerliner modulus of the six models
could exceed levels observed after up to seven years of service when tires were exposed to 500
hours of LTDE roadwheel testing or eight weeks of capped-inflation oven aging. The 22 addi-
tional tire models subjected to three to eight weeks of oven aging with vent and refilled inflation
showed average changes in innerliner/innermost layer modulus in the shoulder and bead region
that were within the ranges of values observed in in-service tires. It is hypothesized that the ob-
served changes in innerliner modulus during service or accelerated aging may affect the liner’s
permeability and/or flexibility over time.[1]
Future evaluations of accelerated aging tests will examine possible correlations between the in-
nerliner properties of each tire model documented in this report to each tire model’s whole-tire
performance in proposed accelerated aging tests.
viii
BACKGROUND
Tires of six of the models used in this paper were collected from on-vehicle service in Phoenix,
Arizona and analyzed by NHTSA during development of an accelerated tire durability test.[2]
Scientific literature primarily attributes the changes in properties of the rubber compounds and
their interfaces to other components to thermal-oxidation.[4-15] A key tire component affecting
thermal-oxidation in tires is the innerliner since it slows the diffusion of oxygen from the pressu
rized tire cavity through the tire structure during service. As explained by Niziolek, Nelsen, &
Jones (2000):
“The innerliner is one of the most critical components affecting the durability of tubeless
pneumatic tires. The function of the innerliner is to provide an effective barrier that main
tains the correct inflation pressure and also minimizes the flow of oxygen and water va
por from the inflation air through the tire structure. Maintaining the correct inflation pres
sure is related to the diligence of the vehicle owner/operator but is greatly facilitated by
the effectiveness of the innerliner as an air barrier by avoiding the need for frequent air
pressure checks and adjustments. To preserve carcass integrity the flow of inflation air
and accompanying oxygen and water vapor into interior components of the tire must be
minimized in order to prevent separations and failures due to the buildup of intracarcass
pressure, and oxygen and water induced degradation and loss of adhesion.”[14]
Several authors have described the effect of liner composition on liner permeability.[3,16-17]
These studies have also demonstrated the effects of liner permeability and liner gauge on intra
carcass pressure and inflation pressure retention. The effect of compound variables on innerliner
permeability has been studied.[17-19] Coddington (1979) examined correlations between inner-
liner permeability, oxidation, and belt edge durability during roadwheel testing.[3] Tokita, Sig
worth, Nybakkan, & Ouyang (1985) concluded that liner permeability and gauge had a strong
influence on the generation of belt edge separations in radial tires.[20] Waddell (2006-07) found
strong correlations between innerliner permeability, or whole tire air loss rate, on intra-carcass
pressurization, belt edge separation, and time to failure in roadwheel durability test (both with
and without accelerated aging), among tires of the same design with varied innerliner formula
tions.[21-26] However, he found no correlation between inflation pressure loss rate and perfor
mance in a stepped-up load roadwheel test across dissimilar models of new tires from different
manufacturers.[24,26] Therefore, the research implies that construction features of the tire
beyond innerliner permeability and air loss rate also strongly factor into the performance of the
tire during roadwheel testing.
TEST TIRES
In-Service (Field) Tires

The field tires consisted of six brands with a wide age range collected from Phoenix, Arizona
(the NHTSA Phoenix Tire Dataset).[2] The “DOT age” variable was the time between the tire’s
production date and collection date. The mileage was based on odometer reading at collection
date for original equipment (OE) tires. Mileage was estimated for replacement tires by using the
average number of miles per year accumulated on the vehicle multiplied by the age of the tire.
Oven Aged Tires

A wide variety of oven aging conditions were evaluated during the multiple phases of the test
program. For some tires, a pre-oven roadwheel break-in was applied. The break-in used in the
earliest phase of test development was 50/50 O2/N2 inflation, maximum sidewall pressure, max
imum sidewall load, for 24 hours at 75 mph. A subsequent phase used air inflation, sidewall
pressure corresponding to maximum sidewall load, maximum sidewall load, for 23 hours at 50
mph. The final phase used air inflation, sidewall pressure corresponding to maximum sidewall
load, maximum sidewall load, for 2 hours at 50 mph. The tires were oven-aged from 2 to 12
weeks at 55�C to 70�C using 50/50 O2/N2 inflation gas. The inflation pressure used in the earliest
phase of test development was the maximum pressure listed on the sidewall. Later phases used
the pressure that corresponded to the maximum sidewall load from the Tire & Rim Association
or equivalent tables. The tire cavity pressure was either capped, which allowed the pressure and
gas composition to change over the test period, or the inflation gas was replenished weekly, by
vent and re-inflate.
Wheel-Tested (LTDE and P-END) Tires

Two roadwheel tests were evaluated. The first roadwheel aged endurance test was the Long
Term Durability and Endurance (LTDE) test. The LTDE test was developed by Michelin and
shared with NHTSA.[27] The roadwheel hours on the LTDE test were varied by NHTSA from
100 to 508 hours, which was thought to impart 1-5 years of equivalent aging. The second method
is called the Passenger Tire Endurance (P-END) test. The P-END test was developed by Conti
nental Tire and submitted to NHTSA on a confidential basis. The details of the methods will not
be discussed in this paper. The roadwheel hours on the P-END test were varied by NHTSA from
96 to 240 hours, which was also thought to impart 1-5 years of equivalent aging.
EXPERIMENTAL TECHNIQUES
The tires were dissected to remove the innerliner compound for testing. The innerliner compound
was taken from the inside tire surface in a slice that was typically about 0.5-1 mm (20-40 mil)
thick. The innerliners from the three groups of tires were subjected to the following chemical and
physical analyses:
Fourier Transform Infrared Spectroscopy (FTIR)

This method provided polymer identification.[28,29] Polymer identification was performed by
FTIR (ASTM D 3677-90 [1995]) using a Perkin Elmer Spectrum BX Spectrometer. Transmit
tance was measured as a function of wavelength using a sodium chloride crystal. The polymers
were identified two ways, by the examination of pyrolysis products or cast films. The sample
was extracted with an organic solvent to remove the organic additives (plasticizers, antioxidants,
antiozonants, waxes, oils, etc.) and purify the polymers. The polymer is then thermally degraded
and the resulting pyrolyzate is examined using infrared spectroscopy. For cast film samples, the
polymer was dissolved in a suitable solvent, filtered, and cast on a sodium chloride plate. The
infrared spectra were compared to known reference spectra that have been generated at ARDL to
identify the polymers. Figure 1 shows the FTIR equipment and test sample. The use of FTIR for
polymer identification is well known.[30-35]
Figure 1. FTIR Test

Equipment Test Sample
Beilstein
This chemical test is a qualitative flame that was used to determine whether halogens are present.
In this study, the test was used to detect the presence of chlorine or bromine halogens (i.e., chlo
ro- or bromo-butyl rubber) in the innerliner compound.
Energy Dispersive X-ray Spectroscopy (EDAX)

This chemical test was used to identify chlorine, bromine and zinc levels semi-quantitatively.
The sample was prepared by placing the tire innerliner on an aluminum pin mount coated with
double-sided carbon adhesive tape. EDAX was used in conjunction with the scanning electron
microscope providing chemical analysis (Figure 2). EDAX can detect all elements except H, He,
Li, and Be. Tire innerliners were analyzed using a Cambridge S150T SEM interfaced with an
EDAX PV9800 X-ray detector and IXRF EDS2004 X-ray analysis computer software. The
Backscatter Detection (BSD) mode was used for imaging. Energy Dispersive X-ray (EDX) anal
ysis was done on elements above Sodium (Na) in the periodic table in the energy range from 0
KeV to 20 KeV. The x-ray spectral lines were calibrated using a copper/aluminum standard to
assure correct identification of the elements. Automatic baseline correction is used and only
those elements above the background matrix are reported. Results should be considered as being
semi-quantitative. It should be kept in mind that only an area approximately 1.1 mm2 was being
analyzed, and the sample may not be homogenous over a larger area. The beam energy used was
20 KeV, which would penetrate the surface to a depth of about 7µm. The results reflect the rela
tive amounts of the elements present in the surfaces of the samples to this depth. All samples
were analyzed in the same manner using ZAF correction for the semi-quantitative analysis at a
sample tilt of 20�. Contained in Figure 2 is an EDX spectrum of a sample. All data for each sam
ple was normalized to 100%.
Figure 2. SEM/EDAX Test

Test Equipment Output
X-ray Fluorescence (XRF)

The method used a Jordan Valley EX-3600M TEC Laboratory Spectrometer for qualitative de
termination of solid samples for elements of atomic mass greater than sodium (Figure 3).[36,37]
The results are reported in three different concentration groups, i.e. major (>1%), minor
(100ppm-1%), traces (<100ppm). The sample was placed into a disposable cup. The X-ray
source was a palladium tube using a 45kV accelerating voltage. One set of spectra was the result
of analysis with a titanium target. In the titanium secondary target analysis, the source was
pointed at the target and the target element was excited and fluoresced. Then the target fluores
cence was used to excite the sample. The titanium target increased the sensitivity for the light
elements (see figure). This was utilized for the analysis and detection of the following elements
(Sulfur, Silicon, Potassium, and Calcium). The second sets of spectra were analyzed with a Col
limator. A collimator was placed between the source and sample to reduce signal (background).
This technique was also used to determine remaining elements (Bromine, Iron, Zinc, and Chlo
rine) (see figure). The elements contained in the sample are thereby excited to emit the element-
specific X-ray fluorescence radiation. A liquid nitrogen cooled light element detector (LED)
Si(Li) measured the fluorescent and scattered x-rays from the sample as a multichannel analyzer
and software assigned each pulse an energy value, thus producing the spectrum.
Figure 3. XRF Test

Test Equipment Output for Light ElementsOutput for Heavy Elements
Pyrolysis-Gas Chromatography/Flame Ionization Detector (GC/FID)

This test method provided quantification of butyl rubber, natural rubber, polybutadiene rubber,
and styrene butadiene rubber in rubber compounds.[38,39] The analytical system consisted of a
PerkinElmer Clarus 500 GC/FID interfaced with a CDS Analytical Pyroprobe 5000 Pyrolysis
Autosampler (Figure 4). Samples were loaded into the pyroprobe and rapidly pyrolyzed at
550�C. The volatiles and degradation products were automatically introduced into the GC carrier
stream and transferred to the GC column equipped with a non-polar capillary column for analysis
by GC/FID. Only monomer peaks (isobutylene, isoprene, styrene, and butadiene) having the
highest intensity were used for the calibration. A piece of sample about 0.5 mg was used. To
have sufficient separation between isobutylene and 1,3 butadiene, the GC oven was cooled down
to -20�C, using liquid nitrogen. The test’s duration was about 40 minutes. The detection limits
are about +/-5 weight percent for the polymer components in the formulation. The peak assign
ments and calibration are in the discussion section.
Figure 4. Pyrolysis GC/FID Test

Test Equipment Loading Sample into Pyroprobe
Pyrolysis-Gas Chromatography/Mass Spectroscopy (GC/MS)

This method also provided quantification of butyl rubber, natural rubber, polybutadiene rubber,
and styrene butadiene rubber in rubber compounds.[40-48] The analytical system consisted of a
PerkinElmer Clarus 500 GC/ 560D MS interfaced with a CDS Analytical Pyroprobe 5000 Pyro
lysis Autosampler. Samples were rapidly pyrolyzed at 550�C. The volatiles and degradation
products were automatically introduced into the GC carrier stream and transferred to the GC col
umn equipped with a non-polar capillary column for analysis by GC/MS. A piece of sample
about 0.2 mg was used. The tests duration was about 40 minutes. The detection limits are about
+/-5 weight percent for the polymer components in the formulation. The peak assignments and
calibration are in the discussion section.
Thermal Gravimetric Analysis (TGA)

TGA is a useful tool for characterizing polymers.[49-54] TGA has been utilized to characterize
the polymer type in blends.[55] The weight loss as a function of temperature has been used to
determine polymer loading, rubber chemical loading, carbon black loading and ash levels. For
polymers with very different thermal stabilities, the TGA curves can be used to determine the
amount of each polymer present. Thermogravimetric analysis (TGA) was performed using about
10 mg of sample (Figure 5). The purge (He) gas flow rate to the TGA was set at 10ml/min during
weight loss measurements. The heating rate was 10�C/min to improve the resolution of small
variations in the decomposition curves. At 600�C, the purge gas was switched over to air for car
bon black combustion. The total analysis time was approximately 1.5 hours.
Figure 5. TGA Test

Test Equipment Loading Sample
Extraction
Solvent extraction with acetone was used to remove non-polymerized organic components. Ex
tractable content was measured per ASTM D297-93 with acetone solvent. To perform the analy
sis, a sample was placed in a paper thimble and extracted for 16 hours with acetone at reflux
conditions using an extraction apparatus (Figure 6). The solvent removed plasticizers, processing
aids, organic accelerators or their decomposition products, fatty acids, antioxidants, antiozonants,
resins, free sulfur, and other organic additives. The extractable content was used in the calcula
tion of the rubber hydrocarbon content (RHC).
Figure 6. Extraction Test

Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-AES)

Inductively Coupled Plasma (ICP) – Atomic Emission Spectroscopy (AES) was used to quantita
tively determine inorganic content. The metal contents were determined according to ASTM D
1971-02. Atomic emission spectroscopy (AES) used quantitative measurement of the optical
emission from exited atoms to determine their concentration. The sample was ashed and dis
solved in acid. The metals were acid digested on a hot plate to solubilize the elements of interest.
The digested solutions were pumped into the plasma as a liquid stream at the rate of about 1 mL
per minute with a peristaltic pump and introduced to the Spectro FTP-08 ICP Analyzer (Figure
7). The solution was aspirated into the excitation region where they were desolvated, vaporized,
and atomized in Argon plasma. All the compounds are dissociated and yield atomic emission
spectra. The inductively coupled plasma (ICP) was at a very high temperature (7000-8000�K) for
excitation. The high temperature atomization source promoted the atoms into high energy levels.
The atoms decay back to lower levels by emitted light. Since all atoms in the sample were ex
cited simultaneously, they can be detected simultaneously. The results are reported in parts per
million of the sample, typically quantitative analysis of 21 elements.
Figure 7. ICP-AES Test

Pump Starting Test
Oxygen Content (Fixed Oxygen by Weight)

This method measures oxygen content (elemental oxygen analysis) of an organic material ex
pressed in weight percent of elemental oxygen per weight of sample. The equipment is a Perkin
Elmer PE 2400 Oxygen Elemental Analyzer with furnace temperature of 1200�C, carrier gas
He/H2, and specimen size of 2 mg. The calibration involves purging the unit with carrier gas
(He/H2) for 10 to 30 minutes and running three (3) blanks to get an average blank value. Then
run three (3) benzoic acid standards to determine the calibration coefficient. The samples were
tested after establishing the blank (correction) and calibration coefficient.
Permeability
The innerliner sample’s permeability to gas transmission was measured at two temperatures
(21�C and 65�C). Method ASTM D1434-82, procedure V was used.[56-60] The units on per
meability are cubic centimeter oxygen at STP 1-cm/cm2-sec atm. The apparatus by which per
meability was measured works on the principles described by G. J. van Amerongen.[60] The gas
cell is made of two parts of steel, containing gas chambers separated from each other by a rubber
membrane (Figure 8). The testing was performed with either a 66.4 cm2 or an 8.04 cm2 surface
area permeability cell. The gas was introduced into the lower chamber. The upper chamber was
1
Standard Temperature and Pressure of 273K (0°C) and 1 atmosphere (101.325 kPa)
connected to a volume gauge. The volume changes were recorded and permeability calculated
using the equations in ASTM D1434.
Figure 8. Permeability Test

Test Equipment Sample and Fixture
Microscopy
Microscopy measurements were used to determine innerliner thickness. Measurements were tak
en on tire “omega” sections (a cross-section of the tire from bead to bead). All measurements
were taken on scanned, polished cross-sections using measurement software and NIST-traceable
calibration standards (Figure 9). The individual component thicknesses in each cross-section
were measured and entered into Excel spreadsheets.
Figure 9. Microscopy
Test Equipment Micrograph of a Tire Cross-Section
Indentation Modulus
Indentation modulus profiling was conducted to map the modulus (akin to hardness) of the rub
ber compound across the thickness of the innerliner. The indentation modulus measurements (for
modulus profiling) were performed in accordance with the methodology published by Gillen,
Terrill, & Winter (2001). The equipment in Figure 10 was used to acquire indentation modulus
measurements of the rubber components in 0.1 mm increments from interior to exterior surface
of the region studied (innerliner to tread for the shoulder region, innerliner to sidewall for bead
region). Test specimens were obtained with minimal heat input in an embedment medium suita
ble for grinding and polishing in order to obtain a flat surface for measurement. A single radial
scan was performed on tread tire in the shoulder of the crown and the lower sidewall at the rim
flange.
Figure 10. Modulus Profiling Test

Test Equipment Schematic
Probe Probe in Contact with Sample
ASTM D 2240 Type A Durometer Hardness

Durometer hardness measurements were conducted on the innerliner to measure the bulk hard
ness of the innerliner components as an indicator of initial cure and state of oxidation. Two in
nerliner samples were measured from each tire, one sample from the centerline of the crown at 0
degrees from the Tire Identification Number (TIN or “DOT Code”), and one sample from the
centerline of the crown at 180 degrees from the TIN. Five ASTM D 2240 Type A Durometer
hardness measurements were performed on each sample.
10
INNERLINER FORMULA RECONSTRUCTION

To estimate the composition of the innerliner compound a variety of steps are necessary. An in
nerliner compound contains a variety of components, however the type of materials and their
functions are generally known in the industry. There are numerous techniques that can be used in
concert to provide complementary information to estimate the components of a rubber com
pound. These include such general categories as:
• Measuring the amount of ingredients by physical separation of the components, for in
stance by volatility using pyrolysis or thermogravimetric analysis (TGA), or solubility us
ing solvent extraction. The separated components can be subjected to further analysis.
• Measuring the energy emission or absorption of atoms or chemical groups. For instance,
x-ray emission spectroscopy measuring the characteristic energy released by an atom
struck by x-rays, or Fourier transform infrared spectroscopy (FTIR) measuring the ab
sorption of infrared energy corresponding to specific chemical bonding.
• Measuring the interaction of a component with a medium. For instance, gas chromato
graphy (GC) measuring the interaction with a defined surface as molecules in the gas
phase are moved along.
• Measuring the reaction of a component. For instance, the Beilstein test turns a flame
green when a copper wire has been reacted with a compound containing halogen.
• Measuring the size or mass of a component. For instance, mass spectrometry (MS) corre
lating the molecular mass of a component with its reaction to a magnetic field.
By combining techniques, either in series (e.g. pyrolysis/GC/MS) or in parallel (TGA and FTIR)
there are a wide variety of ways to determine composition of a compound. The analytical tech
niques used in this study are only a small sampling of those available, and new techniques with
greater sensitivity and selectivity are being introduced to the field on a regular basis.
A typical model compound formulation is shown in Table 1 below.[62] Rubber compounds are
normally specified in parts per hundred rubber (phr), where the amount of rubber is set to 100,
and all other components are specified as a ratio to the amount of rubber. The percent by weight
is also shown for comparison. Using this compound as an example, the process used to estimate
the formulation of the innerliners in this study is shown in Table 2. Detailed explanations of the
test techniques are found in the Experimental Techniques section of this report. It should be
noted that the materials were identified based on well-known compounding practices. For in
stance, the presence of isobutylene groups and bromine atoms is assumed to indicate the use of
bromobutyl polymer, and not some heretofore-unknown use of isobutylene rubber and a bromi
nated flame retardant in a tire innerliner.
11
Table 1. Model Innerliner Formulation
Ingredient phr % by weight

Brominated Polyisobutylene Rubber (HIIR) 70 30.77
Natural Rubber (NR) 30 13.19
Carbon Black 60 26.37
Clay 40 17.58
Stearic Acid 1 0.44
Processing Oil 10 4.40
Tackifier Resin 15 6.59
Zinc Oxide 5 2.20
Sulfur 0.5 0.22
Accelerator 1 0.44
Total 227.5 100
Table 2. Analyses Used in Formula Reconstruction Estimates for Innerliner Compounds

Compound Analysis Technique Employed Comments
Thermal Gravimetric Analysis (TGA) is used to es Base amount of polymer and phr carbon
timate the amount of: black determined. Total parts per hun
• moisture, stearic acid, processing oil, anti dred (phr) of volatile and inorganic ma
oxidants, antiozonants, unreacted sulfur, ac terial determined.
celerator fragments, and tackifier resin
• polymer, including small amounts of reacted
sulfur and accelerator
• carbon black
• inorganic material, in this example zinc oxide
and clay.
Inductively Coupled Plasma-Optical Emission Spec The phr of zinc oxide, clay, talc or cal
troscopy (ICP-AES) of inorganic ash quantitatively cium carbonate determined.
determines elements present:
• zinc Ł zinc oxide
• aluminum Ł clay (aluminosilicate)
• magnesium Ł talc (magnesium silicate)
• calcium Ł calcium carbonate
Solvent extraction with acetone to remove non- Type of polymer(s) identified.
polymerized organic components, such as processing
oil, tackifier resin, etc., followed by dissolving the
polymer and analysis by Fourier Transform Infrared
Spectroscopy (FTIR).
Pyrolysis/Gas Chromatography/Mass Spectroscopy Provides best quantitative data for ratio
(GC/MS). of polymer type in compound.
Energy Dispersive X-ray Spectroscopy (EDAX) Identifies chlorine, bromine and zinc
semi-quantitatively.
12
Beilstein test. Presence of chlorine or bromine identi

fied.
Energy Dispersive X-Ray Fluorescence Spectroscopy Identifies chlorine or bromine semi-
(XRF). quantitatively.
Pyrolysis/Gas Chromatography/Flame Ionization De Provides quantitative data for ratio of
tection (GC/FID). polymer type in compound.
Oxygen Content of innerliner. Determines elemental oxygen content
per weight of sample. Can be used as an
indicator of oxidation of the material.
Physical Analysis Technique Employed Comments
Permeability of innerliner sample. Measures the permeation of gas through
the innerliner material using ASTM
D1434 protocols.
Microscopy of tire cross-section to measure innerlin Innerliner thickness varies throughout
er thickness. the bead-to-bead cross-section of a tire.
The location(s) of each microscopy
measurement must be consistent from
sample to sample.
Indentation modulus profiles of tire shoulder region. Measures innerliner modulus (akin to
hardness) values at the shoulder. Can be
used to map the modulus of the com
pound across the thickness of the inner-
liner. Indicator of the state of cure for
new tires and can track the evolution of
modulus properties across the compo
nent profile.
ASTM D 2240 Type A Durometer hardness at the Yields the overall hardness of the inner-
innerliner centerline. liner sample. Indicator of the state of
cure for new tires and can track the evo
lution of bulk hardness properties.
REGRESSION ANALYSIS
Statistical software JMP professional edition version 5 release 5.0.1.2 was used to correlate the
properties to the variables. The variables included tire age (in years), mileage (miles), and the
interaction term (age*mileage). For example, JMP regression was used to determine the best
model for innerliner indentation modulus of tires in service.
RESULTS
Part I - Model Liner Compound Chemical Analysis

Model innerliner compounds were analyzed by chemical analysis, including oxygen content,
TGA, ICP-AES, EDAX, and FTIR. The model compounds are shown below (Table 3-Table 6).
Although these techniques were quite illustrative, newer techniques (including pyrolysis-gc/ms)
13
were used later in this report to more precisely characterize the compositions of liners extracted
from tires.
Table 3. Model Bromobutyl/Natural Rubber Liner Compounds

Compound Liner Liner Liner Liner Liner Liner Liner
1 2 3 4 5 6 18
Ingredient parts parts parts parts parts parts parts
Bromobutyl (BIIR) Exxon 100.00 80.00 60.00 50.00 40.00 20.00 95.00
grade 2222
Natural Rubber (SMR 20) 20.00 40.00 50.00 60.00 80.00 5.00
N660 Carbon Black 60.00 60.00 60.00 60.00 60.00 60.00 60.00
Naphthenic oil, Calsol 810 8.00 8.00 8.00 8.00 8.00 8.00 8.00
or equivalent
Struktol 40MS 7.00 7.00 7.00 7.00 7.00 7.00 7.00
SP 1068 Resin 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Stearic Acid 1.00 1.00 1.00 1.00 1.00 1.00 2.00
Magnesium Oxide 0.15 0.15 0.15 0.15 0.15 0.15 0.19
Zinc Oxide 1.00 1.00 1.00 1.00 1.00 1.00 1.31
Sulfur 0.50 0.50 0.50 0.50 0.50 0.50 0.65
MBTS (mercapto benzo 1.25 1.25 1.25 1.25 1.25 1.25 1.58
thiazyl sulfenamide)
Total 182.90 182.90 182.90 182.90 182.90 182.90 184.73
14
Table 4. Model Chlorobutyl/Natural Rubber Liner Compounds

Compound Liner Liner Liner Liner Liner Liner
7 8 9 10 11 19
ingredient parts parts parts parts parts parts
Chlorobutyl Rubber (CIIR) Exxon- 100.00 80.00 75.00 60.00
Mobil Grade 1066
Natural Rubber (SMR 20) 20.00 25.00 40.00 100.00
Butyl Exxon (IIR) grade 365 (or 100.00
equivalent)
N660 60.00 50.00 60.00 50.00 60.00 60.00
Nonblack Filler, CACO3 40.00 40.00
Naphthenic oil 8.00 5.00 8.00 8.00
Paraffinic Processing Oil, Flexon 876 4.00 4.00
Struktol 40MS 7.00 10.00 7.00 10.00 7.00 7.00
SP 1068 Resin 4.00 7.00 4.00 4.00
Tackifying Resin, Escorez 1102 4.00 4.00
Stearic Acid 1.00 1.00 7.00 1.00 2.00 1.00
Magnesium Oxide 0.15 0.20 7.00 0.20
Zinc Oxide 1.00 3.00 3.00 3.00 5.00 5.00
Sulfur 0.50 0.50 0.50 0.50 2.00 1.50
MBTS 1.25 1.50 1.50 1.50 0.50
Accelerator, Vultac 5 0.20 0.20
TMTD (tetramethylthiuram disulfide) 1.00
CBS (cyclohexyl benzothiazyl sulfe 1.50
namide)
Total 182.90 214.40 198.00 214.40 189.50 188.00
15
Table 5. Model Bromobutyl/SBR Liner Compounds

Compound Liner 13 Liner 14 Liner 15 Liner 16 Liner 17
ingredient parts parts parts parts parts
Bromobutyl Exxon grade 2222 95.00 90.00 70.00 50.00
SBR (SBR 1712) 6.88 13.75 41.25 68.75 137.50
Natural Rubber (SMR 20)
N660 60.00 60.00 60.00 60.00 60.00
naphthenic oil 8.00 8.00 8.00 8.00
aromatic oil 8.00
Struktol 40MS 7.00 7.00 7.00 7.00
SP 1068 Resin 4.00 4.00 4.00 4.00
Stearic Acid 2.00 2.00 2.00 2.00 2.00
Magnesium Oxide 0.19 0.19 0.19 0.19
6PPD 2.00
TMQ 1.00
Zinc Oxide 1.31 1.38 1.62 1.88 3.00
Sulfur 0.65 0.68 0.81 0.93 2.50
MBTS 1.58 1.65 1.80 2.05
Santocure MOR 2.00
Total 186.61 188.65 196.67 205.80 217.00
Table 6. Six Additional Model Compounds for Liner Permeability Testing

L21150 L21150 L21150 L21150 L21150 L21150
Compound
154-1 154-2 154-3 154-4 154-5 154-6
ingredient parts parts parts parts parts parts
Bromobutyl Exxon
100.00 80.00 80.00
grade 2222
CIIR 1068 100.00 80.00
NR (SMR 20) 20.00 100.00 20.00
SBR (SBR 1712) 27.50
N660 60.00 60.00 60.00 60.00 60.00 60.00
naphthenic oil 8.00 8.00 8.00 8.00 8.00 8.00
Struktol 40MS 7.00 7.00 7.00 7.00 7.00 7.00
SP 1068 Resin 4.00 4.00 4.00 4.00 4.00 4.00
Stearic Acid 2.00 1.00 2.00 1.00 2.00 1.00
Magnesium Oxide 0.15 0.15 0.15 0.15 0.15
Zinc Oxide 1.00 1.00 1.00 5.00 3.00 3.00
Sulfur 0.50 0.50 0.50 1.50 0.50 0.50
MBTS 1.20 1.25 1.25 1.50 1.50
CBS 1.50
Total 183.85 182.90 191.40 188.00 186.15 185.15
16
Acetone Extraction of Model Liner Compounds

Model innerliner compounds were analyzed by acetone extraction to determine rubber chemical
levels (Table 7). The acetone extraction results were comparable to the rubber chemical values
determined by TGA technique.
Table 7. Acetone Extraction of Model Liner Compounds

Compound 1 2 3 4 5 6 7 8 9 10
Acetone Extraction (Wt %) 6.68 6.47 9.99 6.45 7.31 6.65 6.22 8.1 9.41 6.83
Oxygen Content of Model Liner Compounds

Five model compounds were analyzed for oxygen content (Table 8). For reference, only the dif
ferences in compound formulations are listed in the table. Holding all other ingredients constant,
innerliner samples using 100 parts of halobutyl rubber had the lowest oxygen content.
Table 8. Oxygen Content of Model Liner Compounds

Compound 1 3 5 7 9
Bromobutyl (BIIR) Exxon grade 2222 (parts) 100.00 60.00 40.00 -
Chlorobutyl Rubber (CIIR) ExxonMobil Grade 1066
- 100.00 75.00
(parts)
Natural Rubber (SMR 20) (parts) - 40.00 60.00 - 25.00
Naphthenic oil (parts) 8.00 5.00
SP 1068 Resin 4.00 7.00
Stearic Acid 1.00 7.00
Magnesium Oxide 0.15 7.00
Zinc Oxide 1.00 3.00
MBTS 1.25 1.50
Oxygen Content (Wt %) 1.52 2.11 1.81 1.71 2.14
ICP-AES of Model Liner Compounds

Five model compounds were analyzed by ICP (Table 9). The zinc level varied with the recipe
zinc oxide (ZnO) loading. The magnesium level was approximately related to the recipe magne
sium oxide (MgO) loading. The titanium, aluminum, nickel, and sodium levels seemed to be re
lated to the butyl loading, possibly from catalyst residues. Phosphorous appeared to be related to
the natural rubber loading. Phosphorous is a catalyst in the biosynthesis of natural rubber latex.
17
Table 9. Ash Composition of Model Liner Compounds

Element Liner 1 Liner 3 Liner 5 Liner 7 Liner 9
1 Aluminum, ppm 64.10 238.60 76.06 89.25 58.65
2 Antimony, ppm < 2.50 < 2.85 < 2.30 3.74 14.42
3 Arsenic, ppm 6.70 4.64 17.02 2.34 < 3.26
4 Berylium, ppm < 0.01 < 0.02 < 0.01 < 0.01 < 0.03
5 Bismuth, ppm < 2.33 < 2.65 < 2.14 < 2.04 < 4.46
6 Boron, ppm 2.10 2.31 1.20 2.01 2.76
7 Cadmium, ppm < 0.43 < 0.49 < 0.40 < 0.38 < 0.82
8 Calcium, ppm 695.17 594.68 447.11 639.38 388.69
9 Chromium, ppm < 1.04 < 1.19 < 0.96 < 0.91 < 2.00
10 Cobalt, ppm < 1.63 < 1.86 < 1.50 < 1.43 < 3.12
11 Copper, ppm 12.56 6.81 4.36 29.72 23.63
12 Iron, ppm 25.00 57.79 44.75 61.76 63.50
13 Lead, ppm < 0.87 < 1.00 < 0.80 < 0.77 1.94
14 Magnesium, ppm 366.19 479.01 75.83 58.17 574.64
15 Manganese, ppm < 0.60 < 1.72 3.08 5.53 < 1.15
16 Nickel, ppm 3.12 3.03 1.14 14.08 5.59
17 Phosphorous, ppm < 33.34 < 110.50 126.20 < 29.20 146.47
18 Potassium, ppm 44.56 163.30 138.47 92.21 184.69
19 Selenium, ppm 4.97 10.48 28.08 17.71 47.12
20 Silicon, ppm 249.97 375.36 179.32 99.88 60.52
21 Silver, ppm < 2.80 < 3.20 < 2.58 < 2.46 < 5.38
22 Sodium, ppm 183.49 177.81 94.88 328.75 190.11
23 Thallium, ppm < 13.89 < 15.83 < 12.78 < 12.17 < 26.65
24 Titanium, ppm 3.09 8.59 4.35 2.41 2.77
25 Vanadium, pm 4.65 5.99 3.76 13.79 2.63
26 Zinc, ppm 1763.29 3810.31 9533.74 4889.45 14375.45
TGA of Model Liner Compounds

Five model compounds were analyzed by TGA. The weight loss curves (Figure 11) and weight
loss derivative curves (Figure 12) showed differences with change in polymer composition. Lin
er 1 (100% bromobutyl) had the highest decomposition temperature. Liner 7 (100 phr chloro
butyl) had similar decomposition temperatures. Liner 9 (25 phr natural rubber), liner 3 (40 phr
natural rubber), and liner 5 (60 phr natural rubber) exhibited lower decomposition temperatures
in that order. Natural rubber content reduced the decomposition temperature. The derivative
curves showed the growth of a peak at about 375�C which increased with natural rubber level.
Addition of natural rubber increased the decomposition temperature of the carbon black, for
which no explanation is known.
From the TGA data, the level of rubber chemicals, polymer, carbon black, and ash were assessed
(Table 10) and compared to the formulation values (Table 11). The rubber chemical levels were
determined by the weight losses before the polymer weight loss began (as indicated by the
18
change in slope associated with rapid loss from polymer). The carbon black levels were the
weight losses above 515�C. The ash levels were the weight after heating to 800�C. The agree
ment between TGA calculated values for polymer and ash levels were very close. The TGA cal
culated values for rubber chemicals and carbon black differed from the actual levels. Presuma
bly, not all of the rubber chemicals were removed at the lower temperatures. In future work, ex
traction will be used for the rubber chemical levels, thereby yielding proper carbon black levels
by calculation.
Figure 11. Overlay Plot of the TGA Weight Loss Curves
120
liner 1
100
liner 3
80
liner 5
Weight (%)
liner 7
60 liner 9
40
20
0
0 100 200 300 400 500 600 700 800
Temperature (deg C)
Figure 12. Overlay Plot of the TGA Derivative Curves
-1
Derivative (wt%/min)
-3
liner 1
-5
liner 3
liner 5
-7
liner 7
-9 liner 9
-11
0 100 200 300 400 500 600 700 800
Temperature (deg C)
19
Table 10. TGA Compositional Analysis (wt%)
rubber chemicals 6.6 6.9 5.8 9.2 6.3
polymer 55.8 56 58.2 54.9 58.0
carbon black 37 36.2 34.7 35.0 33.8
ash 0.66 0.78 1.26 0.79 1.84
Table 11. Actual Compositional Analysis (wt%)

rubber chemicals 11.8 11.8 11.8 11.8 11.7
polymer 54.7 54.7 54.7 54.7 54.0
carbon black 32.8 32.8 32.8 32.8 32.4
ash 0.70 0.71 0.71 0.71 1.78
Eighteen model compounds were analyzed by TGA as standards for tire innerliner polymer iden
tification. The model compound compositions are shown in Table 3-Table 5. The TGA deriva
tive curves were characteristic of the polymers, and used in polymer identification of the tire in
nerliners (Figure 13-Figure 16).
Figure 13. TGA Derivative Curves for Model Compounds 1, 18, 2, 3, 4, 5, and 6.
Increasing Levels of Natural Rubber with Bromobutyl
-1
-3
liner 1
-5 liner 18
liner 2
-7 liner 3
liner 4
-9 liner 5
liner 6
-11
-13
0 100 200 300 400 500 600 700 800
Temperature (deg C)
20
Figure 14. TGA Derivative Curves for Model Compounds 7, 8, 9, 10: Increasing
Levels of Natural Rubber with Chlorobutyl
1
-1
-3
liner 7
liner 8
-5
liner 9
liner 10
-7
-9
-11
0 100 200 300 400 500 600 700 800
Temperature (deg C)
Figure 15. TGA Derivative Curves for Model Compounds 1, 13, 14, 15, 16, 17:
Increasing Levels of oil-extended SBR with Bromobutyl
-1
liner 1
-3
liner 13
liner 14
-5
liner 15
liner 16
-7
liner 17
-9
-11
0 100 200 300 400 500 600 700 800
Temperature (deg C)
21
Figure 16. TGA Derivative Curves for Model Compounds 1, 7, 11:
Bromobutyl, Chlorobutyl and Butyl Rubber
-1
-3
-5 liner 1
liner 7
-7 liner 11
-9
-11
0 100 200 300 400 500 600 700 800
FTIR of Model Liner Compounds

Five model compounds were analyzed by FTIR. The composition summary is shown in Table 12
and Figure 17. The results were qualitative only, not quantitative. The polyisoprene peaks were
observed at 3024, 1660, 1126, 1086, and 831 wave number with increasing absorbance, sequen
tially with natural rubber loading (liner 9, liner 3, and liner 5). The presence of natural rubber at
25 phr loading in liner 9 was scarcely detectable. For this reason, subsequent work used pyroly
sis-gc/fid and pyrolysis-gc/ms to quantify the polymer levels in the innerliner compounds.
Table 12. FTIR Analysis
Compound Polymer Identification

1 Halobutyl
3 Halobutyl & Polyisoprene
7 Halobutyl
22
Figure 17. FTIR of Model Liner Compounds 1, 3, 5, 7, 9
Liner #1 Liner #3
100 90
90 80
80
70
Transmission (%)
Transmission (%)
70
60
60
50
50
40
40
30
30
20 20
10 10
4000 3600 3200 2800 2400 2000 1600 1200 800 400 4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wave Number (cm-1) Wave Number (cm ) -1
Liner #5 Liner #7
90 100
80 90
80
70
Transmission (%)
Transmission (%)
70
60
60
50
50
40
40
30
30
20 20
10 10
4000 3600 3200 2800 2400 2000 1600 1200 800 400 4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wave Number (cm-1) Wave Number (cm-1)
Liner #9
100
90
80
Transmission (%)
70
60
50
40
30
20
10
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wave Number (cm-1)
23
Beilstein of Model Liner Compounds
Five model compounds (1, 3, 5, 7, and 9) were analyzed by Beilstein (qualitative flame identifi
cation test for halogens). The results were slight positive (for the presence of halogen) for all the
five model compounds.
XRF Analysis of Model Liner Compounds

Six model compounds were analyzed by X-ray Fluorescence (XRF) (Table 13). Calibration
curves were determined from the model compound data (Figure 18 & Figure 19). The results
were grouped in categories: Major (>1%), Minor (<100 ppm to 1%), Trace (<100 ppm) by per
cent weight in the sample (wt/wt).
Table 13. XRF Analysis Results of Model Compounds
Barcode Bromine Chlorine Sulfur Calcium Iron Potassium Zinc

Liner #1 Major Major Minor Trace Major
Liner #4 Major Major Minor Trace Minor Major
Liner #7 Minor Major Minor Trace Minor Major
Liner #9 Minor Major Minor Trace Minor Major
Liner #11 Major Minor Trace Major
Liner #19 Major Trace Trace Minor Major
*Grouped in categories: Major (>1%), Minor (<100 ppm to 1%), Trace (<100 ppm)
Figure 18. Correlation between XRF Bromine Content and phr Bromobutyl
(major)
10
1
(trace) (minor)
Bromine (%)
0.1
0.01
0.001
(zero)
0.0001
0 20 40 60 80 100
BIIR (phr)
24
Figure 19. Correlation between XRF Chlorine Content and phr Chlorobutyl
10
(major)
1
(trace) (minor)
Chlorine (%)
0.1
0.01
0.001
(zero)
0.0001
0 20 40 60 80 100
CIIR Content (phr)
EDAX of Model Liner Compounds

Five model compounds were analyzed by EDAX (Table 14). The zinc levels correlated with the
ZnO in the compound. The bromine intensity correlated with the phr of bromobutyl (Figure 20)
and the chlorine intensity correlated with chlorobutyl loading (Figure 21).
Table 14. EDAX of Model Compounds
Liner 1 Liner 3 Liner 5 Liner 7 Liner 9

Element Intensity (c/s) Intensity (c/s) Intensity (c/s) Intensity (c/s) Intensity (c/s)
Silicon 37.6 58.3 63.5 32.0 20.6
Sulfur 455.3 525.4 1083.9 705.3 652.2
Chlorine 368.7 264.6
Potassium 17.5 11.0
Calcium 62.1 40.0 26.8 28.2 19.5
Zinc 76.2 68.8 122.8 63.4 161.8
Bromine 31.4 17.6 13.8
25
Figure 20. Correlation between Bromine Intensity and phr Bromobutyl
40
Bromine Intensity (c/s)

35
bromobutyl
30
25
20
15
10 y = 0.311x + 0.138
5 R2 = 0.996
0
0 20 40 60 80 100
phr Bromobutyl
Figure 21. Correlation between Chlorine Intensity and phr Chlorobutyl
400
Chlorine Intensity (c/s)
350 chlorobutyl
300
250
200
150
100 y = 3.637x - 0.628
50 R2 = 0.999
0
0 20 40 60 80 100
phr Chlorobuty
Part II - Chemical Analysis of the Innerliner from Six Tire Models Retrieved
from Service in Phoenix, AZ
The six tire models that were retrieved from on-vehicle service in Phoenix, AZ are shown in Ta
ble 15. New tires of each tire model were used for innerliner analysis.
26
Table 15. List of Six Phoenix-Retrieved Tire Models

Tire Contains
Tire Description Market Size Tire #
Type Overlay
B B F Goodrich Touring T/A P195/65R15 OE Pass No 1001-1100
C Goodyear Eagle GA P205/65R15 OE Pass Yes 1501-1600
D Michelin LTX M/S P235/75R15 OE Pass No 1101-1200
E Firestone Wilderness AT P265/75R16 OE Pass No 1301-1400
Kelly Pathfinder ATR A/S
H Repl LT Some* 1201-1300
LT245/75R16/E
L General Grabber ST 255/65R16 OE Pass Yes 1401-1500
*The presence of overlays in the Type H light truck tires is build date dependent.
Acetone Extraction of the Six Phoenix Tire Models

The innerliners from six tire models were analyzed by acetone extraction to determine rubber
chemical levels (Table 16). The acetone extraction results were comparable to the rubber chemi
cal values determined by TGA technique.
Table 16. Acetone Extractables (wt%) of the Six Phoenix Tire Models
Tire Number 1030 1132 1227 1337 1427 1530
NHTSA Tire Type B D H E L C
Acetone extractable (wt%) 7.35 6.88 8.12 6.72 11.11 8.13
ICP-AES of the Six Phoenix Tire Models

The six tire innerliners were analyzed by ICP (Table 17). The results suggest that the zinc levels
were similar to model compounds, while some tire innerliner silicon levels were significantly
higher.
Table 17. ICP-AES Analysis of the Six Phoenix Tire Models

Tire Number 1037 1137 1237 1335 1437 1537
Element
Silicon, ppm 89.15 1348.63 3076.23 853.25 871.57 2025.03
Zinc, ppm 15910.67 8480.03 15960.17 30118.67 17864.00 9841.87
TGA of the Six Phoenix Tire Models

Six tire innerliners were analyzed by TGA (Table 18). From the TGA data, the levels of rubber
chemicals, polymer, carbon black, and ash were assessed (Table 12). The polymer composition
results were not quantitative. For that reason, the tire innerliner polymer composition work was
switched to pyrolysis-gc/fid and pyrolysis-gc/ms.
27
Table 18. TGA Compositional Analysis of the Six Phoenix Tire Models (wt%)
Tire Number 1030 1132 1227 1337 1427 1530
rubber chemicals 8.8 8.8 9.8 7.9 7.6 12.5
polymer 56.3 55.5 50.2 49.7 51.0 49.0
carbon black 33.7 32.5 35.4 39.5 39.5 34.7
ash 1.17 3.20 4.64 2.93 1.89 3.76
Beilstein and FTIR of the Six Phoenix Tire Models

The six tire innerliners were analyzed by Beilstein and FTIR (Table 19). All of the six tire inner-
liners were positive for halogen. The polymer compositions results were not quantitative.
Table 19. Beilstein and FTIR Results
Tire Number NHTSA Tire Type Polymer Identification

1037 B Halobutyl Rubber
1137 D Halobutyl Rubber
1237 H Halobutyl Rubber
1335 E Halobutyl Rubber and 10-20 phr SBR
1437 L Halobutyl Rubber
1537 C Halobutyl Rubber
XRF Analysis of the Six Phoenix Tire Models

The six tire innerliners were analyzed by X-ray Fluorescence (XRF) (Table 20). The X-ray fluo
rescence data was used to determine the halogen type in the butyl polymer. The results were
grouped in categories: Major (>1%), Minor (<100 ppm to 1%), Trace (<100 ppm) by weight in
the sample. Note that no evidence of chlorine was found in the samples.
Table 20. XRF Analysis Results

NHTSA
Barcode Tire Bromine Sulfur Calcium Iron Potassium Zinc Silicon
Type
1030 B Major Minor Minor Minor Trace Minor Minor
1132 D Major Minor Minor Minor Minor
1227 H Major Minor Minor Minor Minor
1337 E Major Minor Minor Minor Major
1427 L Major Minor Minor Minor Trace Minor
1530 C Major Minor Minor Minor Minor
*Grouped in categories: Major (>1%), Minor (<100 ppm to 1%), Trace (<100 ppm)
28
EDAX of the Six Phoenix Tire Models

The six tire innerliners were analyzed by EDAX (Table 21). The results (Table 22) suggest that
tire D innerliner is 100-phr bromobutyl and tires B, E, H, L, and C are based primarily on bro
mobutyl. The EDAX results (Table 23) indicate the element levels are in the range of those of
the model compounds, with the exception of the higher silicon levels in some tire innerliners.
Also, Ti, Fe, and Cu were observed in some tire innerliners. Ti and Fe could be polymerization
catalyst residues.
Table 21. EDAX Results for Chlorine and Bromine Analysis

Tire Number 1037 1137 1237 1335 1437 1537
Intensity Intensity Intensity Intensity Intensity Intensity
Element (c/s) (c/s) (c/s) (c/s) (c/s) (c/s)
Chlorine 0.0 0.0 0.0 55.9 0.0 0.00
Bromine 23.6 32.9 16.8 26.4 17.5 25.53
Table 22. EDAX Prediction for Chlorobutyl and Bromobutyl

Tire Number 1037 1137 1237 1335 1437 1537
polymer phr phr phr phr phr phr
chlorobutyl 0.2 0.2 0.2 15.5 0.2 0.17
bromobutyl 76 105 53 84 56 82
Table 23. EDAX Results for Other Elements Analysis

Tire Number 1037 1137 1237 1335 1437 1537
Intensity Intensity Intensity Intensity Intensity Intensity
Element (c/s) (c/s) (c/s) (c/s) (c/s) (c/s)
Si 105 127 356 186 128 276
S 950 788 801 604 811 679
K 0 31 0 0 31 15
Ca 55 61 103 92 51 55
Ti 0 0 169 0 0 133
Fe 0 13 17 11 10 10
Cu 12 11 12 14 13 11
Zn 65 84 103 196 93 66
Part II - Chemical Analysis of the Innerliners from Addition Tire Models

An additional thirty seven tire innerliners (Table 24) were analyzed by acetone extraction, TGA,
X-ray fluorescence or EDAX, pyrolysis-gc/fid, and pyrolysis-gc/ms. Also, the six tire models
from the original NHTSA dataset were included in the pyrolysis-gc/fid and pyrolysis-gc/ms ana
lyses.
29
Table 24. Thirty Seven Additional Production Tires Models Analyzed by Extraction, TGA,
XRF, Pyrolysis-GC/MS
Barcode Tire Plant Market Tread Man. Brand Model Size Load Speed
Type Code Design Range Rating
2012 P1 UT Repl. All Cooper Futura [Pep Dakota H/T P265/75R16 114 S
Season Boys]
2039 P2 UP Repl. All Cooper Futura [Pep Scrambler A/P LT235/85R16 120 N
Season Boys] (LT) (E)
2040 P3 UT Repl. All Cooper Futura [Pep Scrambler A/P P235/75R15XL 108 S
Season Boys] (P-XL)
2065 U2 EU OE Run Goodyear Dunlop SP Sport 4000 P225/60R17 098 T
Flat DSST (Run
Flat)
2113 G1 PD Repl. Winter Goodyear Goodyear Ultra Grip P235/75R15XL 108 S
2126 G2 PJ Repl. All Goodyear Goodyear WRANGLER LT235/85R16 120 R
Season SilentArmor (E)
2135 R2 XL OE All Pirelli Pirelli Scorpion STR LT265/75R16 123 R
Season (E)
2140 Y2 CC Repl. All Yokohama Yokohama Geolandar LT285/75R16 122 Q
Season A/T+II (D)
2165 N1 UP Repl. Winter Cooper Nokian Hakkapeliitta LT235/85R16 120 -
10LT (E)
2178 N2 YL Repl. Winter Nokian Nokian Hakkapeliitta LT265/75R16 119 -
LT (D)
2212 B4 EJ Repl. All Bridgestone Bridgestone DUELER A/T LT285/75R16 122 Q
Season 693 (D)
2226 B6 7X OE All Bridgestone Bridgestone DUELER H/T P245/70R16 106 S
Season 689
2250 B7 VN OE All Bridgestone Firestone Wilderness AT I P265/75R16 114 S
Season
2269 B1 EP Repl. Winter Bridgestone Bridgestone Blizzak DM-Z3 235/75R16 105 Q
2270 B8 0B OE All Bridgestone Bridgestone B450 P205/65R15 092 S
Season
2313 O5 U9 Repl. All Cooper Big O [Big MERIT FOUR P195/65R15 089 S
Season O Tire] SEASON Black
2326 O3 UP Repl. All Cooper Big O [Big ASPEN P205/65R15 092 S
Season O Tire]
2339 O1 PJ Repl. All Goodyear Big O [Big BIGFOOT A/T LT235/85R16 120 Q
Season O Tire] (LT235) (E)
2352 O2 PJ Repl. All Goodyear Big O [Big BIGFOOT A/T LT265/75R16 123 Q
Season O Tire] (LT265) (E)
2365 O4 UT Repl. All Cooper Big O [Big X/T BIG FOOT LT265/75R16 123 N
Season O Tire] (356) (E)
2378 D2 PJ Repl. All Goodyear Arizonian Silver Edition P195/65R15 089 S
Season [Discount
Tire]
2391 D3 U9 Repl. All Cooper Dominator All Season P205/65R15 092 S
Season [Discount
Tire]
2404 D6 PB Repl. All Goodyear Mohave RS P205/65R15 092 R
Season [Discount
Tire]
2417 D5 UP Repl. All Cooper Dominator Sport A/T LT265/75R16 123 Q
Season [Discount (E)
Tire]
2429 D4 3D Repl. All Cooper Dominator Durango Radial LT285/75R16 122 N
Season [Discount A/T (D)
Tire]
30
2438 J1 PJ Repl. All Goodyear Kelly Safari SJR LT265/75R16 112 -

Season (C)
2456 C3 A3 OE All Continental Continental CONTITRAC P235/70R16 104 T
Season
2469 M1 B7 Repl. All Michelin Michelin Cross Terrain P265/75R16 114 S
Season SUV
2482 M3 ED Repl. Winter Michelin Michelin X-Ice 205/65R15 094 Q
2495 C5 AC OE All Continental Continental TouringContact P205/65R15 092 T
Season AS
2501 B9 7X OE All Bridgestone Bridgestone Duravis M773 II LT265/75R16 123 -
Season (E)
2526 C7 A3 OE All Continental Continental Contitrac TR P265/70R17 113 S
Season
2551 C8 P5 OE All Continental General Ameri G4S P205/65R15 092 T
Season
2576 H3 T7 OE All Hankook Hankook DynaPro AS LT245/75R16 120 -
Season (E)
2601 M10 B7 OE All Michelin Michelin LTX A/S LT245/75R16 120 R
Season (E)
2626 S1 V4 Repl. All Sumitomo Sumitomo HTR+ 225/60R16 098 V
Season
2651 T2 9T Repl. All Toyo Toyo 800 Ultra P235/60R16 099 T
Season
Acetone Extraction of Thirty Seven Tire Innerliners

Thirty-seven tire innerliners were analyzed by acetone extraction to determine rubber chemical
levels (Table 25). The acetone extraction results were comparable to the rubber chemical values
determined by the TGA (weight loss) technique.
Table 25. Acetone Extractables (wt%) of Additional Tires

Plant Code Brand NHTSA Barcode Acetone Extraction
0B Bridgestone 2270 9.13%
3D Dominator [Discount Tire] 2429 10.50%
7X Bridgestone 2226 7.69%
7X Bridgestone 2501 8.23%
9T Toyo 2651 8.29%
A3 Continental 2456 9.43%
A3 Continental 2526 9.93%
AC Continental 2495 9.85%
B7 Michelin 2469 5.58%
B7 Michelin 2601 3.59%
CC Yokohama 2140 7.65%
ED Michelin 2482 10.26%
EJ Bridgestone 2212 7.26%
EP Bridgestone 2269 8.18%
EU Dunlop 2065 6.50%
P5 General 2551 11.76%
PB Mohave [Discount Tire] 2404 11.81%
31
PD Goodyear 2113 9.83%

PJ Goodyear 2126 7.98%
PJ Big O [Big O Tire] 2339 8.04%
PJ Big O [Big O Tire] 2352 7.40%
PJ Arizonian [Discount Tire] 2378 11.59%
PJ Kelly 2438 8.83%
T7 Hankook 2576 8.13%
U9 Big O [Big O Tire] 2313 11.89%
U9 Dominator [Discount Tire] 2391 12.13%
UP Futura [Pep Boys] 2039 8.56%
UP Nokian 2165 9.42%
UP Big O [Big O Tire] 2326 10.95%
UP Dominator [Discount Tire] 2417 7.62%
UT Futura [Pep Boys] 2012 11.23%
UT Futura [Pep Boys] 2040 9.99%
UT Big O [Big O Tire] 2365 9.46%
V4 Sumitomo 2626 7.21%
VN Firestone 2250 8.70%
XL Pirelli 2135 7.06%
YL Nokian 2178 7.10%
TGA of Thirty Seven Tire Innerliners

Thirty-seven tire innerliners were analyzed by TGA. The results are summarized in Table 26.
From the TGA data, the level of rubber chemicals, polymer, carbon black, and ash were as
sessed. The polymer composition was qualitatively identified.
Table 26. Composition Analysis by TGA

Polymer Types
Oils (chem Carbon Ash
Plant Polymer
Brand Barcode Butyl NR SBR PBD icals) (wt black (wt
Code (wt %)
(wt (wt (wt (wt %) (wt %) %)
%) %) %) %)
0B Bridgestone 2270 100 9.3 49.8 38.9 2.0
3D Dominator
[Discount 2429 100 7.7 49.8 39.5 3.0
Tire]
7X Bridgestone 2226 100 8.0 52.2 38.1 1.7
7X Bridgestone 2501 100 8.9 49.9 39.1 2.1
9T Toyo 2651 53 47 6.3 48.5 34.5 10.7
A3 Continental 2456 55 45 6.7 51.9 39.5 1.9
A3 Continental 2526 100 8.3 53.0 37.5 1.2
AC Continental 2495 67 33 6.9 51.2 38.8 3.1
32

Polymer Types
Plant Polymer
Code (wt %)
(wt (wt (wt (wt %) (wt %) %)
%) %) %) %)
B7 Michelin 2469 100 8.0 54.0 33.4 4.6
B7 Michelin 2601 100 6.0 55.7 34.1 4.2
CC Yokohama 2140 67 33 6.7 49.6 38.0 5.7
ED Michelin 2482 100 8.6 53.0 35.0 3.4
EJ Bridgestone 2212 100 7.2 50.6 39.3 2.9
EP Bridgestone 2269 100 8.0 50.9 36.4 4.7
EU Dunlop 2065 65 35 7.0 45.2 36.7 11.1
P5 General 2551 54 46 7.9 52.6 36.3 3.2
PB Mohave
[Discount 2404 73 27 11.0 53.5 28.5 7.0
Tire]
PD Goodyear 2113 100 9.5 51.5 36.1 2.9
PJ Arizonian
[Discount 2378 53 47 8.6 53.3 33.2 4.9
Tire]
PJ Big O [Big
2339 100 10.0 49.4 36.1 4.5
O Tire]
PJ Big O [Big
2352 100 9.0 49.3 36.2 5.5
O Tire]
PJ Goodyear 2126 100 7.5 51.1 36.7 4.7
PJ Kelly 2438 100 10.1 48.5 36.6 4.8
T7 Hankook 2576 70 32 5.2 55.0 36.5 3.3
U9 Big O [Big
2313 70 30 7.3 52.4 37.0 3.3
O Tire]
U9 Dominator
[Discount 2391 100 8.8 50.9 37.9 2.4
Tire]
UP Big O [Big
2326 100 8.2 49.0 39.1 3.7
O Tire]
UP Dominator
[Discount 2417 100 7.0 50.5 39.7 2.8
Tire]
UP Futura [Pep
2039 100 7.2 50.3 39.6 2.9
Boys]
UP Nokian 2165 100 6.4 52.2 39.2 2.2
UT Big O [Big
2365 100 8.3 50.1 38.9 2.7
O Tire]
UT Futura [Pep
2012 100 8.4 50.2 37.2 4.2
Boys]
UT Futura [Pep
2040 100 7.0 51.0 38.4 3.6
Boys]
V4 Sumitomo 2626 52 48 5.7 48.8 36.9 8.6
33

Polymer Types
Plant Polymer
Code (wt %)
(wt (wt (wt (wt %) (wt %) %)
%) %) %) %)
VN Firestone 2250 100 8.6 51.1 38.7 1.6
XL Pirelli 2135 61 39 7.3 53.3 29.6 9.8
YL Nokian 2178 62 38 5.8 50.6 29.6 14.0
XRF Analysis of Thirty One Tire Innerliners

Thirty-one tire innerliners were analyzed by X-ray Fluorescence (XRF) (Table 27). The results
were grouped in categories: Major (>1%), Minor (<100 ppm to 1%), Trace (<100 ppm) by
weight in the sample (wt/wt). The calibration curves (Figure 18 and Figure 19) from the model
compounds were used to determine the butyl type (halogen type). The X-ray fluorescence data
was combined with the pyrolysis-gc/fid data to determine the halogen type in the butyl polymer
(Table 32). The halogen type in six of the thirty-seven innerliners was determined by EDAX,
which is discussed in the next section.
34
Table 27. XRF Analysis of 31 Tire Innerliners

Plan
Bar Bro Chlo Sul Cal Potas Sili Tita
t Brand Iron Zinc Tin
code mine rine fur cium sium con nium
Code
0B Bridges- Mi Mi
2270 Major Minor Minor Minor Minor
tone nor nor
3D Dominator
Mi Mi Ma
[Discount 2429 Major Major Minor Minor Major
nor nor jor
Tire]
7X Bridges- Mi Mi
tone nor nor
7X Continental Mi
2501 Major Minor Minor Minor Major Trace
nor
9T Sumitomo Mi Mi
2651 Major Major Minor Minor
nor nor
A3 Bridges- Mi Mi
2526 Major Minor Minor Trace Major Trace
tone nor nor
A3 Kelly Mi Mi
2456 Minor Minor Minor Minor Minor
nor nor
AC Michelin Mi Mi
2495 Major Major Minor Minor
nor nor
B7 Continental Mi Mi
nor nor
B7 Hankook Mi
2601 Major Minor Minor Minor Major Major
nor
CC Yokohama Mi
2140 Minor Minor Minor Minor Major Major
nor
ED Michelin Mi Mi
nor nor
EJ Bridges- Mi
2212 Major Trace Minor Minor Minor Major Major Trace
tone nor
EP Bridges- Mi Mi
2269 Major Minor Minor Minor
tone nor nor
EU Dunlop Mi Mi
2065 Trace Minor Minor Major Minor
nor nor
PD Goodyear Mi Mi
2113 Major Minor Minor Trace Major
nor nor
PJ Big O [Big Mi Mi
O Tire] nor nor
PJ Big O [Big Mi Mi
2352 Major Minor Minor Trace Minor
O Tire] nor nor
PJ Dominator
Mi Mi
[Discount 2438 Minor Minor Minor Minor Minor
nor nor
Tire]
PJ Goodyear Mi Mi
nor nor
T7 General Mi
2576 Major Minor Minor Minor Major Minor
nor
U9 Arizonian
Mi Mi
[Discount 2391 Trace Minor Minor Minor Minor Major
nor nor
Tire]
UP Big O [Big Mi Mi
2326 Major Major Minor Minor Major
O Tire] nor nor
UP Mohave
Mi Mi
[Discount 2417 Major Major Minor Minor Major
nor nor
Tire]
UP Nokian Mi Mi
2165 Minor* Minor Minor Minor Minor Minor
nor nor
UT Big O [Big Mi Mi
2365 Trace Minor Minor Minor Trace Major
O Tire] nor nor
35
UT Futura [Pep Mi Mi

2012 Trace Minor Minor Minor Major
Boys] nor nor
UT Futura [Pep Mi Mi
2040 Trace Minor Minor Minor Minor Major
Boys] nor nor
V4 Michelin Mi
2626 Minor Major Minor Minor Major Minor
nor
XL Pirelli Mi Mi
2135 Major Minor Minor Minor Major
nor nor
YL Nokian Mi
2178 Trace Minor Minor Major Trace Minor Minor
nor
*Suspected outlier, may have missed bromine peak.
EDAX of Six Tire Innerliners (Six Additional Tire Innerliners)

Six tire innerliners were analyzed by EDAX (Table 28-Table 30). EDAX was used to determine
the type of butyl polymer in the tire innerliner. The calibration curves (Figure 20 and Figure 21)
from the model compounds were used to determine the butyl type (halogen type). The EDAX
data was combined with the pyrolysis-gc/fid data to determine the halogen type in the butyl po
lymer (Table 32).
Table 28. EDAX Results (for Bromine and Chlorine)

Plant Code UP VN U9 PJ PB P5
Futura Arizonian Mohave
[Pep Big O [Big [Discount [Discount
Brand Boys] Firestone O Tire] Tire] Tire] General
Barcode 2039 2250 2313 2378 2404 2551
Intensity Intensity Intensity Intensity
Element (c/s) (c/s) (c/s) Intensity (c/s) Intensity (c/s) (c/s)
Chlorine 0.00 34.6 200 17.0 11.1 137
Bromine 24.5 23.3 0.00 3.40 2.84 3.83
Table 29. EDAX Prediction of Tire Innerliner Polymers

Big O Arizonian
Futura [Big O [Discount Mohave [Dis
Brand [Pep Boys] Firestone Tire] Tire] count Tire] General
Barcode 2039 2250 2313 2378 2404 2551
Polymer phr phr phr phr phr phr
Chlorobutyl 0 0 55 0 0 38
Bromobutyl 78 74 0 0 0 0
36
Table 30. EDAX Results (for Other Elements)

Futura Arizonian Mohave
[Pep Big O [Big [Discount [Discount
Brand Boys] Firestone O Tire] Tire] Tire] General
Barcode 2039 2250 2313 2378 2404 2551
Intensity Intensity Intensity Intensity
Element (c/s) (c/s) (c/s) Intensity (c/s) Intensity (c/s) (c/s)
Si 106 83 160 336 694 130
S 759 482 730 839 690 840
K 20 11 14 19 22 21
Ca 61 54 48 79 25 56
Ti 86 124
Fe 16 21 21 14 10 17
Zn 96 165 92 183 162 128
Pyrolysis - Gas Chromatography/Flame Ionization Detector (Pyrolysis-

GC/FID) Analysis of Forty Three Tire Innerliners
Forty-three tire innerliners were analyzed by Pyrolysis-GC/FID. The calibration of the pyrolysis-
gc/fid for polymer identification and quantification included seventeen standards (model liner
compounds). The peak identifications are shown in Table 31 and Figure 22-Figure 24 for SBR
(type1502), BIIR (ExxonMobil 2222), and NR (SMR-L) respectively. The peaks for isobutylene,
isoprene, butadiene, and styrene were used for the calibration curves (Figure 25-Figure 28). The
innerliner analysis results are shown in Table 32. Two tire innerliners were run twice (1030 and
1132) and showed good repeatability. The pyrolysis-gc/fid analysis was combined with XRF
(bromine and chlorine determination) to determine qualitatively the butyl polymer types. The
butyl type in six tires (tire numbers 2039, 2250, 2313, 2378, 2404, and 2551) were determined
by EDAX.
Table 31. Pyrolysis-GC/FID Peak Identification

Chemical Peak Location (min)
Isobutylene 3.9-4.1
Isobutylene trimer (probably) 22.5
Isobutylene trimer (probably) 23.1
Isoprene 8.9-9.1
Isoprene dimer 22.8
Butadiene 4.3
Butadiene dimer 16.99
Styrene 19.95-20.0
37
Figure 22. Pyrolysis-GC/FID Analysis of SBR (1502) Gum Polymer
Figure 23. Pyrolysis-GC/FID Analysis of BIIR Gum Polymer
38
Figure 24. Pyrolysis-GC/FID Analysis of Natural Rubber Gum Polymer
Figure 25. Pyrolysis-GC/FID Calibration Curve for Polyisobutylene Based on

Isobutylene
0.6
Polyisobutylene (gm)
y = 8.804E-08x + 8.905E-03
R2 = 9.639E-01
0.4
0.2
0.0
0 1000000 2000000 3000000 4000000 5000000
Isobutylene Peak Area (uV*sec)
39
Figure 26. Pyrolysis-GC/FID Calibration Curve for Polyisoprene Based on

Isoprene
0.4 y = 3.591E-07x + 5.081E-03
Polyisoprene (gm)
R2 = 9.556E-01
0.2
0.0
0 200000 400000 600000 800000 1000000
Isoprene Peak Area (uV*sec)
Figure 27. Pyrolysis-GC/FID Calibration Curve for Styrene Butadiene Polymer

Based on Styrene
0.35
Styrene Butadine Polymer (gm)
0.30
y = 1.05E-06x - 2.23E-03
0.25 R2 = 9.97E-01
0.20
0.15
0.10
0.05
0.00
0 50000 100000 150000 200000 250000 300000
Styrene Peak Area (uV*sec)
40
Figure 28. Pyrolysis-GC/FID Calibration Curve for Styrene Butadiene Polymer

Based on Butadiene
0.350
Styrene Butadiene Polymer (gm)

0.300
y = 1.39E-06x + 1.46E-03
0.250 R2 = 9.89E-01
0.200
0.150
0.100
0.050
0.000
0 50000 100000 150000 200000 250000
Butadiene Peak Area (uV*sec)
Table 32. Pyrolysis-GC/FID Analysis Summary

Butyl Type
Plant Tire Pyr-GC/FID based
Brand Barcode
Code Type Composition (%) on XRF (or
EDAX)
81/17/2
0B B8 Bridgestone 2270 BIIR
IIR/NR/SBR
Dominator [Discount
3D D4 2429 85/15-IIR/NR BIIR
Tire]
7X B6 Bridgestone 2226 83/17-IIR/NR BIIR
7X B9 Bridgestone 2501 81/19-IIR/NR BIIR
9T T2 Toyo 2651 53/47-IIR/NR BIIR
56/38/6
A3 C3 Continental 2456 BIIR
IIR/NR/SBR
66/21/13
A3 C7 Continental 2526 BIIR
IIR/NR/SBR
A3 L General 1427 70/30-IIR/NR BIIR
61/30/9
AC C5 Continental 2495 BIIR
IIR/NR/SBR
AP B BFGoodrich 1030 #1 100 IIR* BIIR
AP B BFGoodrich 1030 #2 100 IIR* BIIR
B3 D Michelin 1132 #1 100 IIR* BIIR
B3 D Michelin 1132 #2 100 IIR* BIIR
B7 M1 Michelin 2469 100 IIR* BIIR
B7 M10 Michelin 2601 100 IIR* BIIR
CC Y2 Yokohama 2140 72/28-IIR/NR BIIR
41
ED M3 Michelin 2482 89/11-IIR/NR BIIR

EJ B4 Bridgestone 2212 85/15-IIR/NR BIIR
EP B1 Bridgestone 2269 83/17-IIR/NR BIIR
EU U2 Dunlop 2065 70/30-IIR/NR CIIR
M6 C Goodyear 1530 92/6/2-IIR/NR/PBD BIIR
55/37/8
P5 C8 General 2551 CIIR
IIR/NR/SBR
Mohave [Discount
PB D6 2404 82/18-NR/SBR N/A
Tire]
PD G1 Goodyear 2113 93/7-IIR/NR BIIR
Arizonian [Discount
PJ D2 2378 65/35-NR/SBR N/A
Tire]
PJ G2 Goodyear 2126 92/8-IIR/NR BIIR
H Pathfinder [Discount
PJ 1227 84/7/9-IIR/NR/PBD BIIR
Tire]
PJ J1 Kelly 2438 90/8/2-IIR/NR/PBD BIIR
87/11/2
PJ O1 Big O [Big O Tire] 2339 BIIR
IIR/NR/SBR
PJ O2 Big O [Big O Tire] 2352 85/8/7-IIR/NR/PBD BIIR
T7 H3 Hankook 2576 70/30-IIR/NR BIIR
Dominator [Discount
U9 D3 2391 89/11-IIR/NR CIIR
Tire]
73/23/4
U9 O5 Big O [Big O Tire] 2313 CIIR
IIR/NR/PBD
Dominator [Discount
UP D5 2417 83/17-IIR/NR BIIR
Tire]
UP N1 Nokian 2165 83/17-IIR/NR BIIR
UP O3 Big O [Big O Tire] 2326 82/18-IIR/NR BIIR
UP P2 Futura [Pep Boys] 2039 83/17-IIR/NR BIIR
UT O4 Big O [Big O Tire] 2365 86/14-IIR/NR CIIR
UT P1 Futura [Pep Boys] 2012 84/16-IIR/NR CIIR
UT P3 Futura [Pep Boys] 2040 83/17-IIR/NR CIIR
43/47/11
V4 S1 Sumitomo 2626 BIIR
IIR/NR/SBR
VN B7 Firestone 2250 85/15-IIR/NR BIIR
VN E Firestone 1337 86/14-IIR/SBR BIIR
XL R2 Pirelli 2135 72/28-IIR/NR BIIR
48/37/15
YL N2 Nokian 2178 CIIR
IIR/NR/PBD
* Polystyrene resin detected. 1,2
1
e.g., United States Patent 7425591.
2
According to the Polymeric Material Encyclopedia, polymerization of butyl rubber in the presence of chlorinated
polystyrene or poly(styrene-co-butadiene) can provide a compound with special melt and viscoelastic properties that
result in processability improvements. [Salomone, J.C., Editor, 1996, Polymeric Material Encyclopedia, Vol. 1 A
B, p. 897, CRC Press, Inc., Salem, MA].
42
Pyrolysis-gas Chromatography/Mass Spectroscopy (Pyrolysis-GC/MS)
Analysis of Twenty Two Tire Innerliners
Twenty-two tire innerliners were analyzed by Pyrolysis-GC/MS to confirm their compositional
analysis. The seventeen standards (model liner compounds) were analyzed by Pyrolysis-GC/MS
for polymer identification. The peak identifications are shown in Table 33. The peaks for isobu
tylene, isobutylene tetramer, isoprene, isoprene dimer, styrene, and butadiene dimer were used
for the calibration curves (Figure 29-Figure 34). The innerliner analysis is shown in Table 34.
One tire’s innerliner was run twice (2126) and showed good repeatability.
Table 33. Pyrolysis-GC/MS Peak Identification

Chemical Pyrolysis-gc/ms peak location
Isobutylene 2.74-2.83
Isobutylene tetramer 26.78-26.81
Isoprene 7.33-7.60
Isoprene dimer 20.84-20.88
Styrene 18.13-18.15
Butadiene dimer 16.79-16.84
Figure 29. Pyrolysis-GC/MS Calibration Curve for Polyisobutylene Based on

Isobutylene
0.12
0.10 y = 6.573E-11x - 7.763E-03

Polyisobutylene (mg)
R2 = 9.313E-01
0.08
0.06
0.04
0.02
0.00
0.0E+00 5.0E+08 1.0E+09 1.5E+09
Isobutylene Peak Area (uV*sec)
43
Figure 30. Pyrolysis-GC/MS Calibration Curve for Polyisobutylene Based on

Isobutylene Tetramer
0.12
y = 3.862E-10x + 8.460E-04
0.10 2
Polyisobutylene (mg) R = 9.766E-01
0.08
0.06
0.04
0.02
0.00
0.0E+00 1.0E+08 2.0E+08 3.0E+08
Isobutylene Tetramer Peak Area (uV*sec)
Figure 31. Pyrolysis-GC/MS Calibration Curve for Polyisoprene Based on

Isoprene
y = 8.678E-11x - 2.777E-03
0.10
R2 = 9.342E-01
Polyisoprene (mg)
0.05
0.00
0.0E+00 5.0E+08 1.0E+09
Isoprene Peak Area (uV*sec)
44
Figure 32. Pyrolysis-GC/MS Calibration Curve for Polyisoprene Based on

Isoprene Dimer
0.10
y = 6.359E-11x + 1.620E-03
R2 = 9.152E-01
Polyisoprene (mg)
0.05
0.00
0.0E+00 5.0E+08 1.0E+09 1.5E+09
Isoprene Dimer Peak Area (uV*sec)
Figure 33. Pyrolysis-GC/MS Calibration Curve for Styrene Butadiene Polymer

Based on Styrene
0.08
Styrene Butadine Polymer (mg)
y = 2.610E-19x 2 + 2.571E-11x - 6.665E-05

0.06
R2 = 9.979E-01
0.04
0.02
0.00
0.E+00 2.E+08 4.E+08
Styrene Peak Area (uV*sec)
45
Figure 34. Pyrolysis-GC/MS Calibration Curve for Styrene Butadiene Polymer

Based on Butadiene Dimer
0.045
0.040 y = 4.513E-10x + 1.434E-04
Styrene Butadiene Polymer (mg) 0.035 R2 = 9.982E-01
0.030
0.025
0.020
0.015
0.010
0.005
0.000
0.E+00 2.E+07 4.E+07 6.E+07 8.E+07 1.E+08
Butadiene Dimer Peak Area (uV*sec)
46
Table 34. Pyrolysis-GC/MS Analysis Summary

Plant Tire Brand Barcode Pyrolysis-GC/MS Best
Code Type Composition (%)
0B B8 Bridgestone 2270 85/13/2-IIR/NR/SBR
7X B6 Bridgestone 2226 84/16-IIR/NR
7X B9 Bridgestone 2501 81/19-IIR/NR
A3 L General 1427 72/23/5-IIR/NR/PBD
B3 D Michelin 1132 100 IIR*
EP B1 Bridgestone 2269 84/16-IIR/NR
EU U2 Dunlop 2065 75/25-IIR/NR
M6 C Goodyear 1530 92/3/5-IIR/NR/PBD
PJ G2 Goodyear 2126 90/5/4-IIR/NR/SBR
PJ G2 Goodyear 2126 92/7/1-IIR/NR/SBR
PJ H Pathfinder [Discount Tire] 1227 89/4/7-IIR/NR/PBD
PJ J1 Kelly 2438 85/7/8-IIR/NR/PBD
PJ O1 Big O [Big O Tire] 2339 92/4/4-IIR/NR/SBR
PJ O2 Big O [Big O Tire] 2352 87/8/5-IIR/NR/SBR
T7 H3 Hankook 2576 67/33-IIR/NR
U9 D3 Dominator [Discount Tire] 2391 87/11/3-IIR/NR/PBD
U9 O5 Big O [Big O Tire] 2313 78/20/2-IIR/NR/PBD
UT P3 Futura [Pep Boys] 2040 82/18-IIR/NR
V4 S1 Sumitomo 2626 39/51/10-IIR/NR/SBR
VN B7 Firestone 2250 87/13-IIR/NR
VN E Firestone 1337 91/9-IIR/SBR
XL R2 Pirelli 2135 68/32-IIR/NR
YL N2 Nokian 2178 48/38/14-IIR/NR/PBD
*1phr polystyrene resin detected.
In order to estimate the variability of the procedures to measure the polymer content of the inner-
liner, the calculated composition of tires of the same brand were compared. Many samples
showed small amounts of SBR and/or PBD rubber, which could be spurious data, or could come
from small amounts of these polymers that may have been added as recycled rubber. The addi
tion of small amounts of uncured tire compounds (work-away) is less common in modern radial
tires. However, the use of finely ground tire compounds in innerliners is increasing in popularity.
The average formulations were similar by either method of identification (pyrolysis-gc/fid and
pyrolysis-gc/ms). The Bridgestone tires were estimated as an 85/15 bromobutyl/natural rubber
compound. The Continental tires were approximately a 65/35 bromobutyl/natural compound.
The Cooper tires were approximately 85/15 halobutyl/natural formulations, with chlorobutyl or
bromobutyl rubber, varying by plant. The Goodyear tires were approximately a 90/10 bromo
butyl/natural rubber formulation. Finally, the Michelin tires were approximately 100-phr bromo
butyl compound, containing a high styrene resin. These results are summarized in Table 35.
47
Table 35. Summary of Average GC Innerliner Composition by Tire Manufacturer

Tire Brand Number HIIR HIIR NR NR SBR / SBR /
of Content Content Content Content PBD PBD
Samples by FID by MS by FID by MS Content Content
(GC/FID : by FID by MS
GC/MS)
Bridgestone 7 : 6 83.4 ± 2.0 85.3 ± 14.3 ± 6.4 12.9 ± 6.7 2.3 ± 5.2 1.8 ± 3.6
12.8 (SBR) (SBR)
Continental 5 : 1 61.6 ± 6.4 72 31.2 ± 6.8 23 7.2 ± 4.8 5 (PBD)
(SBR)
Cooper 10 : 3 83.1 ± 4.1 82.3 ± 4.5 16.5 ± 3.1 16.3 ± 4.7 0.4 ± 1.3 1.7 ± 1.5
(PBD) (PBD)
Goodyear 7 : 7 89.0 ± 3.7 89.6 ± 2.8 7.9 ± 1.6 5.4 ± 1.9 1.3 ± 2.6 2.0 ± 2.2
(SBR) (SBR)
2.0 ± 2.2 2.9 ± 3.7
(PBD) (PBD)
Michelin 7 : 1 98.4 ± 4.2 100 1.6 ± 4.2 0 0 0
Part IV - Permeability of Model Compounds

Air Permeability of Model Compounds
Model compounds (L21150-154-1 to 6 and liner 2, 4, 5, 6, 7, 8, 9, 10) were analyzed for air per
meability by ASTM method D1434-82 (Table 38). The permeability results from the first six
model compounds were compared to literature values (Table 37).[30,56,60,63] The experimental
results compared closely to literature data. The results were reported in units of cm3STP-cm/cm2
sec-atm, but a conversion table is supplied in Table 36. The testing was performed with a 66.4
cm2 surface area permeability cell and an 8.04 cm2 surface area permeability cell at 21�C and
70�C (Table 38, Figure 35, and Figure 36).
Air Permeability of Ten Model Compounds

The air permeability method (ASTM method D1434-82) was further verified with an additional
twelve model compounds (liners 1-10, 11 and 19) (Table 39 and Table 40). The results were re
ported in units of cm3STP-cm/cm2-sec-atm. The permeability values of the model compounds
were compared to literature values and good agreement was observed. The testing was per
formed with 66.4 cm2 surface area at 21�C and 65�C (Figure 37 and Figure 38).
48
Table 36. Conversion Table

Sample # permeability permeability permeability
(cm3STP-cm/cm2- (cm3STP-cm/cm2- (cm3STP-cm/cm2-
sec-atm) sec-Pa) sec-cmHg)
L21150-154-1(example) 5.30E-09 5.23E-14 6.97E-11
Unit Conversion 1 9.86E-06 1.316E-02
Table 37. Air Permeability Literature Values

Polymer Temperature (�C) Permeability Reference
(cm3STP-cm/cm2-sec-atm)
at 21�C
BIIR 21 3.0E-09 64
BIIR 21 3.6 to 4.6E-9 19
BIIR 25 3.2E-09 17
BIIR 25 3.8E-09 18
BIIR 65 2.7E-08 17
BIIR 65 4.3 to 7.0E-8 64
BIIR 65 2.8E-08 18
NR 21 3.6E-08 64
NR 25 4.2E-08 17
NR 65 2.1E-07 17
49
Table 38. Model Liner Compound Air Permeability Data

Compound # Temperature BIIR CIIR IIR NR SBR Permeability Cell
(deg C) (cm3STP Size
cm/cm2-sec-atm) (cm2)
L21150-154-1 21 100 5.3E-09 66.4
L21150-154-2 21 80 20 9.2E-09 66.4
L21150-154-3 21 80 20 8.1E-09 66.4
L21150-154-4 21 100 5.0E-08 66.4
L21150-154-5 21 100 6.4E-09 66.4
L21150-154-6 21 80 20 9.8E-09 66.4
L21150-154-1 21 100 1.8E-08 8.04
L21150-154-2 21 80 20 1.5E-08 8.04
L21150-154-3 21 80 20 1.3E-08 8.04
L21150-154-3 21 80 20 1.8E-08 8.04
L21150-154-4 21 100 6.4E-08 8.04
L21150-154-5 21 100 2.3E-08 8.04
L21150-154-6 21 80 20 1.9E-08 8.04
Liner 2 70 80 20 3.9E-08 66.4
Liner 4 70 50 50 6.6E-08 66.4
Liner 5 70 40 60 1.3E-07 66.4
Liner 6 70 20 80 1.8E-07 66.4
Liner 7 70 100 3.0E-08 66.4
Liner 8 70 80 20 3.8E-08 66.4
Liner 9 70 75 25 6.4E-08 66.4
Liner 10 70 60 40 1.3E-07 66.4
50
Figure 35. Permeability of Model Compounds at 21�C as a Function of Butyl

Content
7.0E-08
Permeability (cm 3-cm/cm2-s-atm)
6.0E-08 66.4 cm2
8.04 cm2
5.0E-08
Literature
4.0E-08
3.0E-08
2.0E-08
1.0E-08
0.0E+00
0 20 40 60 80 100
Butyl Content (phr)

Content
2.5E-07
Permeability (cm 3 -cm/cm 2-s-atm)
66.4 cm2
2.0E-07
Literature
1.5E-07
1.0E-07
5.0E-08
0.0E+00
0 20 40 60 80 100
Butyl Content (phr)
51
Table 39. 21�C Model Compound Permeability Data (66.4 cm2 Cell Size)
Sample Temperatur phr phr phr phr Permeability
ID e (deg C) IIR CIIR BIIR NR (cm3*cm/(cm2*s*atm
))
Liner #1 21 100 7.04E-09
Liner #2 21 80 20 7.00E-09
Liner #3 21 60 40 2.03E-08
Liner #4 21 50 50 5.53E-09
Liner #5 21 40 60 2.14E-08
Liner #6 21 20 80 4.61E-08
Liner #7 21 100 7.97E-09
Liner #8 21 80 20 8.67E-09
Liner #9 21 75 25 5.25E-09
Liner #10 21 60 40 1.02E-08
Liner #11 21 100 5.03E-09
Liner #19 21 100 5.32E-08
Table 40. 65�C Model Compound Permeability Data (66.4 cm2 Cell Size)
Sample Temperatur phr phr phr phr Permeability
ID e (deg C) IIR CIIR BIIR NR (cm3*cm/(cm2*s*atm
))
Liner #1 65 100 5.23E-08
Liner #2 65 80 20 6.66E-08
Liner #3 65 60 40 1.29E-07
Liner #4 65 50 50 2.22E-07
Liner #5 65 40 60 1.62E-07
Liner #6 65 20 80 2.99E-07
Liner #7 65 100 4.33E-08
Liner #8 65 80 20 7.86E-08
Liner #9 65 75 25 7.17E-08
Liner #10 65 60 40 7.03E-08
Liner #11 65 100 5.09E-08
Liner #19 65 100 4.06E-07
52

Content
7.E-08
Permeabiliyt (cm 3-cm/cm2-s-atm) 6.E-08 66.4 cm2

Literature
5.E-08
4.E-08
3.E-08
2.E-08
1.E-08
0.E+00
0 20 40 60 80 100
Butyl content (phr)

Content
5.E-07
Permeabiliyt (cm -cm/cm 2-s-atm)
66.4 cm2
4.E-07 Literature
3.E-07
3
2.E-07
1.E-07
0.E+00
0 20 40 60 80 100
Butyl content (phr)
53
Part V - Permeability of Innerliners from Production Tires

The innerliners from new tires of each of the six models collected by NHTSA from service in
Phoenix were analyzed for permeability by ASTM method D1434-82 (Table 41). Four or five
tires of each model were analyzed for good repeatability and data confidence. The testing was
performed with the 8.04-cm2 surface area permeability cell at 21�C because of the size limita
tions associated with removing large flat slices of innerliner from tires. The testing was then
conducted on a single tire’s innerliner from each of the thirty-seven tires used in subsequent por
tions of the test development program (Table 42). This testing was then repeated for samples at
65�C to simulate in-service running 1,2 and accelerated oven-aging temperatures (Table 43 & Ta
ble 44). The permeability values of extracted innerliners at 21�C (Figure 39) and 65�C (Figure
40) were plotted against butyl content and compared to literature values.[56,60,63-64] Some data
scatter may come from thickness non-uniformity, as some innerliners have a non-uniform pattern
imprint from the curing bladder that could not be removed. Error bars are shown on the six inner-
liners that had repeat measurements. The confidence was about +/- 25%. The actual permeability
measured for the innerliners at 21�C and 65�C was similar to literature values for compounds
with high butyl content, but measured higher than literature values for compounds with no butyl
content (natural rubber). However, plot against butyl content alone cannot capture the effects of
other constituents in the innerliner such as fillers and oils, which vary from one liner formulation
to another. The average permeability of an innerliner at 65�C was over 500% (6X) higher than its
permeability at 21�C (1.14E-07 versus 1.83E-08 cm^2/(sec*atm)).
1
“Typically, the internal temperature of a tire fitted to a standard passenger car lies between 20 and 90�C, depend
ing on the type of tire, the way the car is driven and the ambient temperature.”, The Pneumatic Tire, Edited by
A.N. Gent and J.D. Walter, The University of Akron, August 2005, p. 490.
2
“A tire operating at normal speeds can achieve internal temperatures in excess of 180°F [82�C].” , Transportation
Research Board Special Report 286, Tires and Passenger Vehicle Fuel Economy, National Research Council of the
National Academies, 2006, p. 33.
54
Table 41. Innerliner Permeability Data at 21�C for the Six Field Tire Models
Plant Tire Barcode Pyrolysis - phr Butyl Gas Permeability (cm^2/(sec*atm))
Code Type GC/FID First Test Second Test Third Test Average Std Dev Confidence
Composition
AP B 1030 100 IIR 100 1.64E-08 1.05E-08 3.14E-09 2.41E-09
1025 1.19E-08 1.33E-08
1026 8.03E-09
1027 7.76E-09 8.37E-09 9.13E-09
1028 7.35E-09 1.26E-08
B3 D 1132 100 IIR 100 1.72E-08 1.00E-08 5.35E-09 4.48E-09
1125 1.47E-08 6.67E-09
1126 1.71E-08 5.56E-09
1127 7.93E-09
1128 6.23E-09 4.81E-09
PJ H 1227 84/7/9 82 1.60E-08 1.04E-08 4.86E-09 4.06E-09
1225 IIR/NR/PBD 1.39E-08
1226 7.05E-09 7.60E-09
1227 1.82E-08 8.29E-09 5.06E-09
1228 7.36E-09
VN E 1337 86/14 86 2.58E-08 1.79E-08 1.13E-08 8.70E-09
1306 IIR/SBR 1.98E-08 5.73E-09
1308 1.90E-08 1.22E-08
1319 4.27E-08 9.06E-09
1333 1.82E-08 8.84E-09
A3 L 1427 70/30 70 2.46E-08 1.82E-08 5.44E-09 4.19E-09
1425 IIR/NR 2.74E-08 1.73E-08
1426 2.02E-08 1.41E-08 1.08E-08
1427 1.70E-08 1.25E-08
1428 1.95E-08
M6 C 1530 92/6/2 92 1.10E-08 1.06E-08 4.41E-09 3.16E-09
1525 IIR/NR/PBD 1.40E-08 9.83E-09
1526 1.46E-08
1527 1.55E-08 1.27E-08 9.50E-09
1528 1.29E-08 4.48E-09
1530 1.96E-09
55
Table 42. Innerliner Permeability Data at 21�C for Subsequent Test Tires
Plant Tire Barcode Pyrolysis -GC/FID phr Gas Permeability
Code Type Composition Butyl (cm^2/(sec*atm))
0B B8 2270 81/17/2-IIR/NR/SBR 81 1.11E-08
3D D4 2429 85/15-IIR/NR 85 2.47E-08
7X B6 2226 83/17-IIR/NR 83 1.18E-08
7X B9 2501 81/19/-IIR/NR 81 1.30E-08
9T T2 2651 53/47-IIR/NR 53 1.86E-08
A3 C3 2456 56/38/6-IIR/NR/SBR 56 1.38E-08
A3 C7 2526 66/21/13-IIR/NR/SBR 66 1.79E-08
AC C5 2495 61/30/9-IIR/NR/SBR 61 2.28E-08
B7 M1 2469 100 IIR 100 1.29E-08
B7 M1 2469 100 IIR 100 1.78E-08
B7 M10 2601 100 IIR 100 2.06E-08
CC Y2 2140 72/28-IIR/NR 72 1.28E-08
ED M3 2482 89/11-IIR/NR 89 1.28E-08
EJ B4 2212 85/15-IIR/NR 85 2.20E-08
EP B1 2269 83/17-IIR/NR 83 2.24E-08
EU U2 2065 70/30-IIR/NR 70 2.76E-08
PB D6 2404 82/18-NR/SBR 0 7.05E-08
PD G1 2113 93/7-IIR/NR 93 1.96E-08
PJ D2 2378 65/35-NR/SBR 0 2.52E-08
PJ D2 2378 65/35-NR/SBR 0 8.39E-08
PJ G2 2126 92/8-IIR/NR 92 1.45E-08
PJ J1 2438 90/8/2-IIR/NR/PBD 92 1.65E-08
PJ O1 2339 87/11/2-IIR/NR/SBR 87 7.93E-09
PJ O2 2352 85/8/7-IIR/NR/PBD 83 5.55E-09
T7 H3 2576 70/30-IIR/NR 70 1.87E-08
U9 D3 2391 89/11-IIR/NR 89 1.65E-08
U9 O5 2313 72/23/5-IIR/NR/PBD 72 2.52E-08
UP D5 2417 83/17-IIR/NR 83 1.18E-08
UP N1 2165 83/17-IIR/NR 83 2.82E-08
UP O3 2326 82/18-IIR/NR 82 1.36E-08
UP P2 2039 83/17-IIR/NR 83 1.50E-08
UT O4 2365 86/14-IIR/NR 86 2.03E-08
UT P1 2012 84/16-IIR/NR 84 1.07E-08
UT P3 2040 83/17-IIR/NR 83 1.66E-08
V4 S1 2626 43/47/11-IIR/NR/SBR 43 2.04E-08
V4 S1 2626 43/47/11-IIR/NR/SBR 43 9.75E-09
VN B7 2250 85/15-IIR/NR 85 2.02E-08
XL R2 2135 72/28-IIR/NR 72 1.65E-08
YL N2 2178 48/37/15-IIR/NR/PBD 47 2.64E-08
YL N2 2178 48/37/15-IIR/NR/PBD 47 1.99E-08
56
Figure 39. Permeability of Tire Innerliners at 21�C as a Function of Butyl Content
8.0E-08
Permeability (cm 2 /sec-atm)
7.0E-08 Tire Innerliners

6.0E-08 Literature
5.0E-08
4.0E-08
3.0E-08
2.0E-08
1.0E-08
0.0E+00
0 20 40 60 80 100
Butyl Content (phr)
57
Table 43. Innerliner Permeability Data at 65�C for Six Field Tire Models
Plant Tire Barcode Pyrolysis - phr Butyl Gas Permeability (cm^2/(sec*atm))
Code Type GC/FID First Test Second Test Third Test Average Std Dev Confidence
Composition
AP B 1030 100 IIR 100 6.26E-08 6.79E-08 6.94E-08 1.79E-08 1.38E-08
1029 9.49E-08 7.96E-08
1031 3.81E-08 6.46E-08
1032 9.42E-08 5.79E-08
1028 6.51E-08
B3 D 1132 100 IIR 100 5.11E-08 6.62E-08 6.57E-08 2.66E-08 2.23E-08
1129 6.35E-08 4.59E-08
1130 1.18E-07 5.23E-08
1131 9.11E-08 3.74E-08
PJ H 1229 82/6/12 82 7.01E-08 4.28E-08 5.92E-08 1.57E-08 1.32E-08
1230 IIR/NR/PBD 4.38E-08 7.22E-08
1231 3.90E-08
1232 8.17E-08 5.97E-08
1226 6.43E-08
VN E 1337 86/14 86 5.78E-08 6.51E-08 2.04E-08 1.70E-08
1357 IIR/SBR 1.07E-07 6.68E-08
1359 5.53E-08
1368 3.57E-08 5.68E-08
1308 7.07E-08 7.03E-08
A3 L 1429 70/30 70 6.29E-08 8.18E-08 9.70E-08 2.78E-08 2.14E-08
1430 IIR/NR 6.03E-08 1.11E-07
1431 1.29E-07 1.04E-07
1432 9.71E-08 8.48E-08
1426 1.42E-07
M6 C 1530 92/6/2 92 4.76E-08 7.95E-08 7.74E-08 2.09E-08 1.40E-08
1529 IIR/NR/PBD 7.27E-08 1.13E-07
1531 4.96E-08 8.08E-08
1532 6.71E-08 8.90E-08 6.92E-08
1527 1.10E-07
1528 7.34E-08
Table 44. Innerliner Permeability Data at 65�C for Subsequent Test Tires
Plant Tire Pyrolysis -GC/FID phr Gas Permeability
Barcode
Code Type Composition Butyl (cm^2/(sec*atm))
0B B8 2270 81/17/2-IIR/NR/SBR 81 5.26E-08
3D D4 2429 85/15-IIR/NR 85 5.21E-08
7X B6 2226 83/17-IIR/NR 83 8.88E-08
7X B9 2501 81/19/-IIR/NR 81 1.36E-07
9T T2 2651 53/47-IIR/NR 53 1.51E-07
A3 C3 2456 56/38/6-IIR/NR/SBR 56 1.61E-07
A3 C7 2526 66/21/13-IIR/NR/SBR 66 5.18E-08
AC C5 2495 61/30/9-IIR/NR/SBR 61 7.52E-08
AC C5 2495 61/30/9-IIR/NR/SBR 61 6.90E-08
B7 M1 2469 100 IIR 100 1.02E-07
B7 M10 2601 100 IIR 100 7.58E-08
CC Y2 2140 72/28-IIR/NR 72 1.22E-07
ED M3 2482 89/11-IIR/NR 89 8.56E-08
58
EJ B4 2212 85/15-IIR/NR 85 1.45E-07

EP B1 2269 83/17-IIR/NR 83 1.80E-07
EU U2 2065 70/30-IIR/NR 70 6.83E-08
PB D6 2404 82/18-NR/SBR 0 4.86E-07
PD G1 2113 93/7-IIR/NR 93 1.57E-07
PJ D2 2378 65/35-NR/SBR 0 5.16E-07
PJ D2 2378 65/35-NR/SBR 0 5.05E-07
PJ O1 2339 87/11/2-IIR/NR/SBR 87 1.62E-07
PJ O2 2352 85/8/7-IIR/NR/PBD 83 1.36E-07
T7 H3 2576 70/30-IIR/NR 70 2.11E-07
U9 D3 2391 89/11-IIR/NR 89 7.31E-08
UP D5 2417 83/17-IIR/NR 83 1.56E-07
UP O3 2326 82/18-IIR/NR 82 1.19E-07
UP P2 2039 83/17-IIR/NR 83 1.66E-07
UT O4 2365 86/14-IIR/NR 86 3.79E-08
UT P1 2012 84/16-IIR/NR 84 1.50E-07
UT P3 2040 83/17-IIR/NR 83 1.20E-07
V4 S1 2626 43/47/11-IIR/NR/SBR 43 1.86E-07
YL N2 2178 48/37/15-IIR/NR/PBD 47 1.35E-07
YL N2 2178 48/37/15-IIR/NR/PBD 47 5.58E-08
Figure 40. Permeability of Tire Innerliners at 65�C as a Function of Butyl Content
7.0E-07
Permeability (cm 2 /sec-atm)
6.0E-07 Tire Innerliners

5.0E-07 Literature
4.0E-07
3.0E-07
2.0E-07
1.0E-07
0.0E+00
0 20 40 60 80 100
Butyl Content (phr)
59
Part VI - Microscopy of Innerliners from Production Tires

The innerliner thickness in the crown region was measured by microscopy in 294 tires, from 40
tire models, from 38 different plants. The average innerliner gauge was computed from three lo
cations (serial side shoulder, tread centerline, and opposite serial side shoulder) and is shown in
Table 45 with the standard deviation. Across the 41 unique tire model/plant code combinations,
the average innerliner thickness in the crown was 0.96 mm, with an average standard deviation
of –0.15 mm. The results displayed graphically in Figure 41 are ordered by manufacturer, plant
code, maximum sidewall pressure, and tire model type designation. In many cases, the higher
inflation pressure light truck tires have thicker innerliners than the passenger tires. When possi
ble, the innerliner placement (i.e. extent of coverage) was determined by visual microscope in
spection of polished omega cuts and generally documents how far down the innerliner coverage
extends. Innerliners can be placed to wrap fully from bead toe to bead toe, or terminate at the
bead toe, or terminate some distance down each sidewall for partial coverage. Often the place
ment was difficult to determine and varied from tire-to-tire, side-to-side in some tire models;
hence the “about xx-yy mm above the toe” terminology in the Innerliner Placement column.
Table 45. Microscopy Innerliner Analysis of Production Tires

Tire Size Plant Tire Data Avg. of Inner- Std. Dev. of Innerliner Placement
Code Type Points liner Thickness Innerliner
(mm) Thickness
(mm)
205/65R15 ED M3 3 1.12 0.09
225/60R16 V4 S1 9 0.94 0.07 Innerliner ends about
3-30 mm above toe
235/75R16 EP B1 3 0.66 0.16
255/65R16 A3 L 96 0.70 0.12 Innerliner wraps
around toe
LT235/85R16 PJ G2 3 0.72 0.04
O1 6 0.99 0.11
UP N1 3 1.22 0.06
P2 6 1.27 0.14
LT245/75R16 B7 M10 9 1.85 0.11 Innerliner wraps
around toe
PJ H 90 1.20 0.27 Innerliner ends about
30 mm above toe
T7 H3 9 0.76 0.07 Innerliner ends at bot
tom of toe or wraps
around toe
LT265/75R16 7X B9 9 1.05 0.17 Innerliner ends about
8-15 mm above toe
60
Table 45. Microscopy Innerliner Analysis of Production Tires

Tire Size Plant Tire Data Avg. of Inner- Std. Dev. of Innerliner Placement
Code Type Points liner Thickness Innerliner
(mm) Thickness
(mm)
PJ O2 6 0.96 0.17
UP D5 3 1.49 0.20
UT O4 3 1.42 0.20
XL R2 6 1.09 0.23
YL N2 3 0.76 0.18
LT285/75R16 3D D4 9 1.23 0.15
CC Y2 3 0.64 0.07
EN B4 3 0.88 0.21
P195/65R15 AP B 162 0.84 0.13 Innerliner ends about
28 mm above toe
PJ D2 6 1.47 0.47
U9 O5 6 0.92 0.15
P205/65R15 0B B8 6 0.74 0.05 Innerliner ends about
11-20 mm above toe
M6 C 113 0.77 0.18 Innerliner ends about
20 mm above toe
P5 C8 9 0.67 0.05 Innerliner wraps
around toe or ends at
bottom of toe
PB D6 3 0.48 0.09
U9 D3 6 0.86 0.14
UP O3 6 0.97 0.15
P225/60R17 EU U2 9 0.68 0.22 Innerliner ends about
13-21 mm above toe
P235/60R16 9T T2 9 0.87 0.16 Innerliner ends about
9-33 mm above toe
P235/75R15XL B3 D 111 0.98 0.14 Innerliner ends at bot
tom of toe
PD G1 3 0.72 0.03
UT P3 15 0.90 0.22 Innerliner wraps
around toe
P245/70R16 7X B6 8 0.91 0.08
P265/70R17 A3 C7 9 0.83 0.08 Innerliner ends about
13-24 mm above toe
P265/75R16 B7 M1 3 1.22 0.12
UT P1 3 1.04 0.12
VN B7 6 0.86 0.23
E 75 0.88 0.27 Innerliner ends about
W2 E 30 0.69 0.15 33 mm above toe
Average by Tire Type & Plant Code 0.96 0.15
61
Figure 41. Microscopy Innerliner Analysis of Production Tires
Part VII - Indentation Modulus of Innerliners from Production Tires

The indentation modulus for all production tires in the study was measured at 0.1mm increments
across the shoulder belt-edge region and bead area, yielding modulus (similar to hardness) results
for all rubber layers in that region, including the innerliner (Figure 42).
62
Figure 42. Indentation Modulus Test Samples and Plots for a Phoenix-Retrieved Tire
Shoulder Region Sample Shoulder Region Plot
15
14
Innerliner 13
12
11
10
Modulus (MPa)
9
shoulder wedge
belt 1 coat
gumstrip
belt 2 coat
8
tread base
tread
7
innerliner
6
plycoat
5
4
3
2
1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Position (mm)
Bead Region Sample Bead Region Plot

40
Innerliner
35
30
25
toeguard
20
toeguard
apex
15
innerliner
plycoat
plycoat
sidewall
innerliner
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12
63
Indentation Modulus - Shoulder Region Innerliner

Indentation Modulus - Shoulder Region Innerliner, In-Service Tires
For the six tire models retrieved from service in Phoenix, AZ (Types B, C, D, E, H, and L), in
nerliners from tires of various ages and mileages were compared to innerliners from new tires of
each model (Figure 43). Five of the six tire models had innerliners from the shoulder region that
exhibited an increase in modulus with increasing age. The correlation coefficient (R2) of the li
near fits was greater than 0.9 in tire types B, C, and L. The indentation modulus of the innerliner
from the tire type D did not increase with age. The aging behavior of the innerliner is almost cer
tainly affected by compounding. Butyl rubber is known to have better oxidation resistance than
SBR and NR polymers, and is thus more resistant to hardening. However, butyl content alone
was not the main determinant. For instance, observe the dissimilar behavior of tire types B and
D, with innerliners thought to both use 100% bromobutyl.
Figure 43. Average Indentation Modulus of Shoulder Region Innerliner as a Function of

Age
The average change of the indentation modulus for the innerliner in the shoulder region of each
of the six Phoenix-retrieved tires is shown in Figure 44 and Table 46. Modulus values ranged
from an initial softening of 0.5 MPa after 0.5 years of service to an increase of up to 1.8 MPa
after 7.4 years of service. The average rate of change in the average innerliner modulus value for
the six tire models was 0.21 MPa/yr of service.
64
Figure 44. Average Change in Indentation Modulus of Shoulder Region Innerliner for Six
Tire Models During Service in Phoenix, AZ
65
Service in Phoenix, AZ
Tire DOT Age Avg. Innerliner Change in Avg. Rate of Change in Avg.
Type (yrs) Modulus (MPa) Modulus (MPa) Modulus (MPa/yr)
B 1.37 2.31 0.02 0.01
2.51 2.90 0.61 0.24
2.53 2.76 0.47 0.19
4.66 3.52 1.23 0.26
6.04 3.66 1.37 0.23
7.38 4.08 1.79 0.24
C 1.81 3.04 0.17 0.09
5.45 3.51 0.64 0.12
D 1.58 3.05 0.60 0.38
3.87 2.44 -0.01 0.00
E 0.53 3.51 -0.56 -1.06
2.91 4.87 0.80 0.27
3.27 5.18 1.11 0.34
H 1.36 2.78 0.81 0.60
1.99 3.15 1.18 0.59
2.99 3.48 1.51 0.51
5.96 2.99 1.02 0.17
L 1.06 3.39 0.29 0.27
1.24 3.57 0.47 0.38
2.65 4.11 1.01 0.38
Average 0.21
Indentation Modulus - Shoulder Region Innerliner, Roadwheel Tested Tires

Thirty-one new tires of the six original tire models collected from service in Phoenix were sub
jected to various durations of the Michelin Long Term Durability Endurance (LTDE) roadwheel
test. In Figure 45 the average change in innerliner modulus in the shoulder region for each model
is plotted against hours on the roadwheel test. The approximate innerliner polymer composition
from Pyrolysis-GC-MS or Pyrolysis-GC-FID analysis is listed with each tire model. As observed
in service, innerliners from the shoulder region in tire types B, C, E, L, and H hardened with in
creasing roadwheel hours and innerliners from the Type D tires exhibited no change. The aver
age modulus change and rates of change are calculated in Table 47 for the in-service tires.
66
Figure 45. Average Change in Indentation Modulus of the Shoulder Region Innerliner
Versus LTDE Roadwheel Hours
Table 47. Average Change in Indentation Modulus of the Shoulder Region Innerliner
During LTDE Testing
Tire Number of Avg. Innerliner Change in Avg. Rate of Change in Avg.
Type Tires Modulus (MPa) Modulus (MPa) Modulus (MPa/100 hrs)
B 6 3.43 1.14 0.40
C 4 3.42 0.55 0.17
D 6 2.51 0.06 0.04
E 7 5.35 1.28 0.33
H 4 3.07 1.10 0.86
L 4 4.20 1.10 0.57
Average 3.74 0.87 0.37
Only five tires were subjected to indentation modulus testing after running on the Continental
Passenger Endurance (P-END) test (Figure 46). Therefore, there were insufficient data to make a
similar analysis of rates of change in the innerliner modulus for the P-END test. Though there
are only five data points, a similar trend to service and LTDE testing is observed in P-END test
ing. Tire Types B, C, E, and L showed an increase in average innerliner modulus during roadw
heel aging, and Type D showed a slight decrease.
67
Figure 46. Average Change in Indentation Modulus of the Shoulder Region Innerliner
Versus P-END Roadwheel Hours
Indentation Modulus - Shoulder Region Innerliner, Oven Aged Tires
New tires of types B, C, D, E, L, and H were subjected to one of three accelerated oven-aging
conditions listed in Table 48 and compared to new, unaged tires of each model. In the initial
phase of test development capped inflation with 50/50 N2/O2 was used (i.e. the tire was filled to
test pressure, valve stem cap installed, and the inflation gas and pressure were not changed
throughout the oven aging sequence).
68
Table 48. Oven Aging Conditions with Capped Inflation Gas - Six Phoenix Tire Models
Name Temp Duration Inflation Inflation Pre-Oven Roadwheel
(�C) (weeks) Gas Maintenance Break-in
Oven - 55C - 12 55 12 50/50 Capped (none) None
wks - 50/50 N2/O2
Capped
Oven - 65C - 8 65 8 50/50 Capped (none) None
wks - 50/50 N2/O2
Capped
Oven - 65C - 8 65 8 50/50 Capped (none) 24 hrs, 75 mph, 100%
wks - 50/50 N2/O2 max sidewall load,
Capped 100% max sidewall
24/75BI- 50/50 pressure, 50/50 N2/O2
inflation
The innerliner in the shoulder region of all six models exhibited some hardening during the
capped oven aging (Figure 47). The approximate innerliner polymer composition from Pyrolysis-
GC-MS or Pyrolysis-GC-FID analysis is listed with each tire model. The average change in
modulus and rate of change in modulus for each test condition are displayed in Table 49. In some
cases, the long capped-inflation oven aging sequences (8-12 weeks) produced larger innerliner
modulus changes than were observed after up to 7 years of service. The rates of change per week
of aging were higher for 65�C oven aging than 55�C.
Some of these test tires were subjected to the third test condition in Table 48 that includes a 24
hour roadwheel break-in prior oven aging. The combination of oven aging after a roadwheel
break-in is called “hybrid aging.” The break-in did not appear to significantly affect the innerlin
er modulus. JMP software effect screening analysis of innerliner indentation modulus showed
that the best model fit was oven temperature and tire type (Figure 48). The effect of aging time
was not significant, probably, in part, because the tire inflation gas was capped during the expe
riment and becomes depleted during the 8-12 weeks of oven aging (Table 50).
69
Figure 47. Average Change in Indentation Modulus of Shoulder Region Innerliner for
Capped-Inflation Oven Aging
Capped-Inflation Oven Aging
Tire Oven - 55C - 12 wks - 50/50 Oven - 65C - 8 wks - 50/50 Oven - 65C - 8 wks - 50/50
Type Capped Capped Capped - 24/75BI- 50/50
Average Average Rate of Average Average Rate of Average Average Rate of
Modulus Change Change Modulus Change Change Modulus Change Change
(MPa) in Mod in Avg. (MPa) in Mod in Avg. (MPa) in Mod in Avg.
ulus Modulus ulus Modulus ulus Modulus
(MPa) (MPa/ (MPa) (MPa/ (MPa) (MPa/
wk) wk) wk)
B 4.01 1.72 0.14 4.60 2.31 0.29 5.20 2.91 0.36
C 3.79 0.92 0.08 4.38 1.51 0.19 4.62 1.75 0.22
D 3.00 0.55 0.05 2.50 0.05 0.01 2.86 0.41 0.05
E 6.06 1.99 0.17 6.29 2.22 0.28
H 2.94 0.97 0.08 3.50 1.53 0.19 3.17 1.20 0.15
L 4.78 1.68 0.14 5.08 1.98 0.25 4.84 1.74 0.22
Average 4.01 1.72 0.14 4.60 2.31 0.29 5.20 2.91 0.36
70
Figure 48. Model Prediction of Innerliner Indentation Modulus with Capped-Inflation Oven
Aging
7
Innerliner_Avg_Mod_MPa Actual
Tire_Type
6 B
C
5
D
4 E
H
3 L
2
1
1 2 3 4 5 6 7
Innerliner_Avg_Mod_MPa Predicted
P<.0001 RSq=0.92 RMSE=0.4218
71
Table 50. Regression Analysis of Innerliner Modulus as a Function of Oven Temperature

and Tire Type
Summary of Fit
RSquare 0.917023
RSquare Adj 0.889363
Root Mean Square Error 0.421798
Mean of Response 3.8628
Observations (or Sum Wgts) 25
Analysis of Variance
Source DF Sum of Squares Mean Square F Ratio
Model 6 35.391664 5.89861 33.1544
Error 18 3.202440 0.17791 Prob > F
C. Total 24 38.594104 <.0001
Scaled Estimates
Nominal factors expanded to all levels
Continuous factors centered by mean, scaled by range/2
Term Scaled Estimate Std Error t Ratio Prob>|t|
Intercept 3.8625222 0.084657 45.63 <.0001
Temperature (degC) 0.8409045 0.098871 8.51 <.0001
Tire_Type[B] 0.0069453 0.177307 0.04 0.9692
Tire_Type[C] 0.0046109 0.191938 0.02 0.9811
Tire_Type[D] -1.207889 0.191938 -6.29 <.0001
Tire_Type[E] 1.6721109 0.191938 8.71 <.0001
Tire_Type[H] -1.015389 0.191938 -5.29 <.0001
Tire_Type[L] 0.5396109 0.191938 2.81 0.0116
Prediction Profiler
Innerliner_Avg_Mod_MPa
6.29
3.869467
1.97
E
C
D
H
B
0
65
44.4
Temperature (degC) Tire_Type
Subsequent phases of the aging test development project subjected an additional 21 tire models
to oven aging conditions that used weekly vent and refill of the 50/50 N2/O2 inflation gas. The
vent and refill procedure was conducted to mitigate the observed depletion of oxygen during the
72
oven aging testing and perhaps shorten the required duration of oven aging. These test conditions
are listed in Table 51.
Table 51. Oven Aging Conditions with Vent and Refill of Inflation Gas - 21 Additional Tire
Models
Name Temp Duration Inflation Inflation Pre-Oven Roadwheel
(�C) (weeks) Gas Maintenance Break-in
Oven - 65C - 8 65 8 50/50 Weekly vent & 23 hrs, 50 mph, 100%
wks - 50/50 - N2/O2 refill max sidewall load, 100%
WRFL - max pressure for max
23/50BI - Air sidewall load, air infla
tion
Oven - 65C - 3 65 3 50/50 Weekly vent & 2 hrs, 50 mph, 100% max
wks - 50/50 - N2/O2 refill sidewall load, 100% max
WRFL - pressure for max sidewall
2/50BI - Air load, air inflation
Oven - 65C - 5 65 5 50/50 Weekly vent & 2 hrs, 50 mph, 100% max
wks - 50/50 - N2/O2 refill sidewall load, 100% max
WRFL - pressure for max sidewall
2/50BI - Air load, air inflation
Twelve new tire models were subjected to a 23-hour roadwheel break-in at 50 mph (80.5 km/h),
with air inflation, at 100% of the maximum rated load and corresponding pressure, followed by 8
weeks oven aging at 65�C with 50/50 N2/O2 inflation that was vented and refilled weekly. The
results are compared to unaged, new tires of each model in Figure 49. Table 52 details the aver
age change in modulus and average rate of change. The average increase in modulus of the in
nerliner in the shoulder region for the twelve tire models was 1.04 MPa, which is well within the
range of values observed for the original six tire models retrieved from service. The average rate
of change in the average innerliner modulus value for the twelve tire models was 0.13 MPa per
week of aging.
73
Figure 49. Change in Average Indentation Modulus of Innerliner in Shoulder Region for 8
Weeks Oven Aging @ 65�C with 23-hour Break-in
74
Table 52. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 8
Tire Mfg. Test Estimated In Tire Average Average Rate of
IP nerliner Com Type Modulus Change in Change in
(kPa) position (MPa) Modulus Avg. Modulus
(MPa) (MPa/wk)
Bridgestone 240 84/16 - BIIR/NR B6 4.47 1.30 0.16
87/13 - BIIR/NR B7 6.64 2.67 0.33
Continental 240 56/38/6 - BI C3 4.67 0.76 0.10
IR/NR/SBR
61/30/9 - BI C5 4.63 -0.16 -0.02
IR/NR/SBR
Cooper 240 78/20/2 - O5 3.44 0.90 0.11
CIIR/NR/PBD
82/18 - BIIR/NR O3 4.17 1.38 0.17
87/11/3 - D3 3.26 0.21 0.03
CIIR/NR/PBD
280 82/18 - CIIR/NR P3 4.17 1.36 0.17
450 85/15 - BIIR/NR D4 4.38 1.60 0.20
550 83/17 - BIIR/NR P2 4.18 1.26 0.16
Goodyear 240 65/35 - NR/SBR D2 2.84 0.03 0.00
550 87/8/5 - BI O2 3.41 1.19 0.15
IR/NR/SBR
Average 4.19 1.04 0.13
The analysis was again completed for an additional 10 tire models were subjected to a 2-hour
roadwheel break-in at 50 mph (80.5 km/h), with air inflation, at 100% of the maximum rated
load and corresponding pressure, followed by 3 or 5 weeks of oven aging at 65�C with weekly
vent and refill of the 50/50 N2/O2 inflation gas. The results are compared to unaged, new tires of
each model in Figure 50 and Table 53. The average increase in innerliner modulus was 1.64 MPa
for the 3-week oven aging condition and 1.45 MPa for the 5-week oven aging condition, which
are again within the range of values observed for tires retrieved from service. The average rate of
change in the average innerliner modulus value for the ten tire models was 0.55 and 0.29 MPa
per week of aging for the 3 week and 5 week oven aging times respectively. It was expected that
the longer oven aging condition (5 weeks) would produce a larger increase in the average inner-
liner modulus than the shorter oven aging condition (3 weeks). However, that was not the case
for this mix of tire types. The tires with high percentages of natural rubber (NR) and/or styrene
butadiene rubber (SBR) in the innerliner were observed to initially harden and then soften with
increased time in the oven. For these innerliners, thermal reversion likely begins to dominate at
the longer oven periods.
75
Figure 50. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 3 or 5
76
Table 53. Change in Avg. Indentation Modulus of Innerliner in Shoulder Region for 3 or 5
Tire Mfg. Tes Estimated Tire Oven - 65C - 3 wks - 50/50 Oven - 65C - 5 wks - 50/50
t IP Innerliner Typ WRFL - 2/50BI - Air WRFL - 2/50BI - Air
kPa Composition e Average Average Rate of Average Average Rate of
Mod Change Change Mod Change Change
ulus in Mod in Avg. ulus in Mod in Avg.
(MPa) ulus Modulus (MPa) ulus Modulus
(MPa) (MPa/wk (MPa) (MPa/wk
) )
Bridges- 240 85/13/2 - B8 6.31 2.27 0.76 6.16 2.12 0.42
tone BI
IR/NR/SBR
550 81/19 - BI B9 4.72 1.73 0.58 4.88 1.89 0.38
IR/NR
Continen 240 55/37/8 - C8 6.07 2.54 0.85 4.47 0.94 0.19
tal CIIR/NR/SB
R
66/21/13 - C7 5.91 3.20 1.07 4.68 1.97 0.39
BI
IR/NR/SBR
Cooper 280 82/18 - P3 4.39 1.07 0.36 4.77 1.45 0.29
CIIR/NR
Goodyear 240 75/25 - U2 5.26 0.98 0.33 5.90 1.62 0.32
CIIR/NR
Hankook 550 67/33 - BI H3 5.46 1.65 0.55 5.17 1.36 0.27
IR/NR
Michelin 550 100 - BIIR M10 3.53 0.26 0.09 3.82 0.55 0.11
Sumitomo 240 39/51/10 - S1 6.31 2.01 0.67 6.54 2.24 0.45
BI
IR/NR/SBR
Toyo 240 53/47 - BI T2 4.19 1.24 0.41 3.36 0.41 0.08
IR/NR
Average 5.14 1.64 0.55 4.96 1.45 0.29
Indentation Modulus - Bead Region Innermost Layer

As documented in Table 45, innerliners can be placed to wrap fully from bead toe to bead toe,
terminate at the bead toe, or terminate some distance down each sidewall for partial coverage.
Therefore, the indentation modulus measurements in the bead region represent the innermost
rubber compound in the bead, not necessarily true innerliner material. The indentation modulus
profile of the bead region was measured for the five of the six tire models retrieved from service
in Phoenix, AZ (Figure 51). No tires of Type C were available for this particular test. The inner
most layer in the Type B did exhibit an increase in average modulus with increasing age. One
Type B tire exhibited an average 4.76 MPa increase in modulus of the innermost layer after 7.38
years of service. The average rate of change in modulus for the six tire models was 0.23 MPa per
year. The test was not performed on tires following P-END or LTDE roadwheel testing.
77
Figure 51. Average Indentation Modulus of Innermost Layer of Bead Region for Five
Phoenix Tire Models
Table 54. Change in Avg. Indentation Modulus of Innerliner in Bead Region During
Service in Phoenix, AZ
Tire DOT Age Avg. Innerliner Change in Avg. Rate of Change in Avg.
Type (yrs) Modulus (MPa) Modulus (MPa) Modulus (MPa/yr)
B 2.53 4.49 1.95 0.77
4.66 3.61 1.07 0.23
7.38 7.3 4.76 0.64
D 1.58 3.29 0.38 0.24
3.87 2.74 -0.17 -0.04
E 2.91 3.93 -0.74 -0.25
H 1.99 2.82 0.7 0.35
L 1.06 3.12 -0.14 -0.13
Average 0.23
New tires of types B, C, D, E, L, and H were subjected to one of three accelerated oven aging
conditions with capped inflation pressure (Table 48) and compared to new, unaged tires of each
model in Figure 52. The average change in modulus and rate are listed in Table 55. The magni
tudes of the changes in modulus observed during capped-inflation oven aging were well within
the range of values observed in field tires.
78
Figure 52. Average Indentation Modulus of Innermost Layer in Bead Region for Capped-
Inflation Oven Aging
Table 55. Average Change in Indentation Modulus of Innermost Layer in the Bead Region
During Capped-Inflation Oven Aging
Tire Oven - 55C - 12 wks - 50/50 Oven - 65C - 8 wks - 50/50 Oven - 65C - 8 wks - 50/50
Type - Capped Capped Capped - 24/75BI- 50/50
Avg. Avg. Rate of Avg. Avg. Rate of Avg. Avg. Rate of
Mod. Change Change Mod. Change Change Mod. Change Change
(MPa) in Mod. in Avg. (MPa) in Mod. in Avg. (MPa) in Mod. in Avg.
(MPa) Mod. (MPa) Mod. (MPa) Mod.
(MPa/ (MPa/ (MPa/
wk) wk) wk)
B 3.36 0.82 0.07 - - - 3.65 1.11 0.14
C 4.38 1.05 0.09 4.14 0.81 0.10 4.62 1.29 0.16
D 3.04 0.13 0.01 3.38 0.47 0.06 3.22 0.31 0.04
E 5.61 0.94 0.08 - - - 4.65 -0.02 0.00
H 2.98 0.86 0.07 2.97 0.85 0.11 3.68 1.56 0.20
L 4.09 0.83 0.07 4.57 1.31 0.16 5.30 2.04 0.26
Avg. 3.91 0.77 0.06 3.77 0.86 0.11 4.19 1.05 0.13
The results for 12 new tire models subjected to 8 weeks oven aging at 65�C with 23-hour roadw
heel break-in are compared to unaged, new tires of each model in Figure 53 and Table 56. The
79
average increase in modulus for the twelve tire models during the 8-week oven aging was 1.30
MPa, which is well within the range of values observed for the six tire models retrieved from
service. The average rate of change in the average innerliner modulus value for the twelve tire
models was 0.16 MPa per week of aging.
Figure 53. Change in Average Indentation Modulus of Innerliner in Bead Region for 8
80
Table 56. Change in Average Indentation Modulus of Innerliner in Bead Region for 8
Weeks Oven Aging @ 65�C with 23-hour Break-in (at 50 mph)
Tire Mfg. Test Tire Average Average Change Rate of Average
IP kPa Type Modulus in Modulus Change in Modulus
(MPa) (MPa) (MPa/wk)
Bridgestone 240 B6 4.69 1.60 0.20
B7 7.54 4.05 0.51
Continental 240 C3 4.58 1.10 0.14
C5 4.70 0.51 0.06
Cooper 240 O5 4.61 1.17 0.15
O3 4.41 1.33 0.17
D3 4.44 0.50 0.06
280 P3 5.37 2.12 0.27
450 D4 4.45 1.47 0.18
550 P2 4.28 0.93 0.12
Goodyear 240 D2 2.72 -0.53 -0.07
550 O2 2.95 0.51 0.06
Average 4.62 1.30 0.16
The analysis was again completed for an additional 10 tire models subjected to 3 or 5 weeks of
oven aging at 65�C with a 2-hour roadwheel break-in (Figure 54 and Table 57). The average in
crease in innerliner modulus was 1.56 MPa for the 3-week oven aging condition and 1.87 MPa
for the 5-week oven aging condition, which are again within the range of values observed for the
six tire models retrieved from service. The average rate of change in the average innerliner mod
ulus value for the ten tire models was 0.52 and 0.36 MPa per week of aging for the 3-week and
5-week aging times respectively. Again, the tires with high percentages of natural rubber (NR)
and/or styrene-butadiene rubber (SBR) in the innerliner were observed to initially harden and
then soften with increased time in the oven. For these innerliners, thermal reversion likely begins
to dominate at the longer oven periods.
81
Figure 54. Change in Average Indentation Modulus of Innerliner in Bead Region for 3 or 5
Weeks Oven Aging @ 65�C with 2-hour Break-in (at 50 mph)
82
Table 57. Change in Avg. Indentation Modulus of Innerliner in Bead Region for 3 or 5
Tire Mfg. Test Tire Oven - 65C - 3 wks - 50/50 Oven - 65C - 5 wks - 50/50
IP Type WRFL - 2/50BI - Air WRFL - 2/50BI - Air
(kPa) Avg. Avg. Rate of Avg. Avg. Rate of
Mod. Change Avg. Mod. Change Avg.
(MPa) in Change (MPa) in Change
Mod. in Mod. Mod. in Mod.
(MPa) (MPa/wk) (MPa) (MPa/wk)
Bridgestone 240 B8 5.98 2.00 0.67 6.68 2.70 0.54
550 B9 4.68 1.73 0.58 4.62 1.67 0.33
Continental 240 C8 5.16 2.44 0.81 4.32 1.60 0.32
C7 6.29 2.70 0.90 4.70 1.11 0.22
Cooper 280 P3 4.63 1.38 0.46 6.02 2.77 0.55
Goodyear 240 U2 7.16 2.31 0.77 7.38 2.53 0.51
Hankook 550 H3 3.63 -0.45 -0.15 4.57 0.49 0.10
Michelin 550 M10 3.64 0.69 0.23 4.07 1.12 0.22
Sumitomo 240 S1 8.91 2.67 0.89 9.81 3.57 0.71
Toyo 240 T2 3.50 0.26 0.09 3.44 0.20 0.04
Avg. 5.29 1.56 0.52 5.60 1.87 0.37
Summary - Indentation Modulus Results
The results of the innerliner analysis are summarized in Table 58. With the exception of the 8
week, capped-inflation pressure oven aging tests, the magnitudes of the average change in inner
liner/innermost layer modulus for the accelerated aging tests were within the range of values ob
served in the six tire models retrieved from service. The tires with high percentages of natural
rubber (NR) and/or styrene-butadiene rubber (SBR) in the innerliner were observed to initially
harden and then soften with increased time in the oven. For these innerliners, thermal reversion
likely begins to dominate at the longer oven periods.
83
Table 58. Summary Table of Average Change and Rate of Change in Innerliner Modulus
by Condition
Tire Models Condition Shoulder Region Bead Region
Avg. Rate of Avg. Avg. Rate of Avg.
Change in Change in Change in Change in
Mod. (MPa) Mod. Mod. (MPa) Mod.
B, C, D, E, H, Service in Phoenix -0.56 to 1.79 0.21 MPa/yr -0.74 to 4.76 0.23 MPa/yr
L
LTDE 0.87 0.37 - -
MPa/100 hrs
Oven - 55C - 12 1.72 0.14 MPa/wk 0.77 0.06 MPa/wk
wks - 50/50
Capped
Oven - 65C - 8 wks 2.31 0.29 MPa/wk 0.86 0.11 MPa/wk
- 50/50 - Capped
- 50/50 - Capped
24/75BI- 50/50
B6, B7, C3, C5, Oven - 65C - 8 wks 1.04 0.13 MPa/wk 1.30 0.16 MPa/wk
D2, D3, D4, - 50/50 - WRFL
O2, O3, O5, 23/50BI - Air
P2, P3
B8, B9, C7, C8, Oven - 65C - 3 wks 1.64 0.55 MPa/wk 1.56 0.52 MPa/wk
H3, M10, P3, - 50/50 - WRFL
S1, T2, U2 2/50BI - Air
- 50/50 - WRFL
2/50BI - Air
CONCLUSIONS
Since the innerliner is the main barrier to permeation of the pressurized inflation gas (containing
degradative oxygen) through the tire, it was desired to know material composition, thickness, and
permeability of a large cross-section of passenger vehicle tire innerliners in order to understand
their influence on whole-tire performance in a tire-aging test. Model innerliner compounds with
known chemical formulations were used to evaluate a wide range of laboratory analysis methods.
A final methodology was developed to allow estimation of innerliner compound formulation.
The analysis indicated that tire innerliners were primarily comprised of polymer blends of halo
butyl (bromobutyl or chlorobutyl), natural (isoprene), styrene butadiene, and polybutadiene rub
ber, with one manufacturer using small amounts of polystyrene resin. The innerliner compounds
also contained varying levels of carbon black, inorganic material (such as clay, zinc oxide, mag
nesium oxide, talc, or calcium carbonate), stearic acid, processing oils, antioxidants, antiozo
nants, unreacted sulfur, accelerator fragments, and tackifier resin. This methodology was applied
to estimate the innerliner composition of six tire models collected from service in Phoenix, AZ,
84
as well as an additional 37 tire models used in subsequent phases of the project. Microscopy of
cross-sections of each tire model was used to measure the thickness of the innerliner at the center
and two edges of the crown region, as well as the amount of coverage of the innerliner. The in
nerliner compounds of the production tires varied significantly in composition, thickness, and
placement, even within the same manufacturer. Across the 41 unique tire model/plant code com
binations, the average innerliner thickness in the crown was 0.96 mm, with an average standard
deviation of –0.15 mm.
Sections of the innerliner were removed from all tire models and measured for permeability at
room temperature (21�C) and approximate in-service running temperature (65�C). The measured
permeability for the innerliners at 21�C and 65�C was similar to literature values for compounds
with high butyl content, but measured higher than literature values for compounds with no butyl
content. The average permeability for an innerliner sample at 21�C increased over 500% when
tested at 65�C (1.14E-07 versus 1.83E-08 cm^2/(sec*atm)). This would imply that the more a
tire is in operation (i.e., where it experiences higher operating temperatures), the faster the per
meation of inflation gas through the innerliner layer. A large amount of scatter was seen in the
permeability data due to the non-uniform pattern imprint on the innerliner left from the curing
bladder. Since average of the three innerliner thickness measurements in the crown ranged from
0.5 to 1.9 mm, shaving slices to smooth uniform thicknesses for permeability testing would be a
major technical challenge. Readers are cautioned that innerliner permeability does not necessari
ly scale to whole tire inflation pressure loss rate, as many other size and construction parameters
affect the whole tire loss rate.
The indentation modulus technique was employed to map the modulus (hardness) profile of the
rubber components in the shoulder and bead region of tires retrieved from Phoenix and used in
accelerated aging experiments. The first topic examined was whether or not the modulus of tire
innerliners changed during service. Results from six tire models retrieved from service in Phoe
nix, AZ indicated that the innerliner in the shoulder region of the tires increased by approximate
ly 0.21 MPa per year, and the innermost layer increased 0.23 MPa per year in the bead region.
Total increases of 1.79 MPa in the shoulder region and 4.76 MPa in the bead region were ob
served. The second topic examined was whether or not the modulus of tire innerliners changed
during accelerated aging and if the magnitudes of the change matched or eventually exceed those
observed during service. For the original six tire models collected in Phoenix, both the roadwheel
and oven accelerated aging tests could produce changes in innerliner modulus that were similar
to those observed in on-vehicle tires. The magnitude of the increase in innerliner modulus of the
six models could exceed levels observed after up to seven years of service after the tires expe
rienced 500 hours of LTDE roadwheel testing or eight weeks of capped-inflation oven aging.
The 22 additional tire models subjected to three to eight weeks of oven aging with vent and re
filled inflation showed average changes in innerliner/innermost layer modulus in the shoulder
and bead region that were within the ranges of values observed in in-service tires. It is hypothe
sized that the observed changes in innerliner modulus during service or accelerated aging may
affect the liner’s permeability and/or flexibility over time.
Future evaluations of accelerated aging tests will examine possible correlations between the in
nerliner properties of each tire model documented in this report to each tire model’s whole-tire
performance in proposed accelerated aging tests.
85
APPENDIX 1. INDENTATION MODULUS INNERLINER DATA, SHOULDER & BEAD
Tire Test Description Barcode DOT Number Age Est. Avg. Shoulder St. Dev. Shoul Avg. Bead In St. Dev. Bead Notes
Type (yrs) Mileage Innerliner Mod der Innerliner nerliner Mod Innerliner Mod
(mi) ulus (MPa) Modulus (MPa) ulus (MPa) ulus (MPa)
B New 1094 APC6BB113803 0 0 2.54 0.65
B New 1040 APC6BB113803 0 0 2.29 0.2
B New 1042 APC6BB113803 0 0 2.29 0.09
B Phoenix 0027 APC6BB114301 1.37 24593 2.31 0.15
B Phoenix 0042 APC6BB113800 2.51 6049 2.9 0.21
B Phoenix 0049 APC6BB213700 2.53 32028 2.76 0.16 4.49 1.36
B Phoenix 0063 APC6BB11308 4.66 27337 3.52 0.12 3.61 0.06
B Phoenix 0002 APC6BB11117 6.04 51392 3.66 0.12
B Phoenix 0064 APC6BB11455 7.38 44385 4.08 0.31 7.3 2.22
B LTDE - 60 mph - 100 hrs 1074 APC6BB113803 0 0 2.44 0.17
B Oven - 55C - 12 wks - 50/50 1081 APC6BB113803 0 0 4.01 0.37 3.36 0.49
Capped
B Oven - 65C - 8 wks - 50/50 1076 APC6BB113803 0 0 4.6 0.25 5.74 Only one data point for
Capped innerliner, not used.
B Oven - 65C - 8 wks - 50/50 1086 APC6BB113803 0 0 5.2 0.48 3.65
Capped - 24/75BI - 50/50
B P-END - 240 hrs 1057 APC6BB113803 0 0 3.18 0.14 Tire failed @ 240 hrs -
Liner Split
B4 Oven - 65C - 8 wks - 50/50 2208 ENLFDAC5204 0 0 4.55 0.2 4.38 0.33 Failed in oven at week 7
WRFL - 23/50BI - Air due to: Sidewall blister
B6 New 2222 7X9LPDW3205 0 0 3.17 0.26 3.09 0.28
B6 Oven - 65C - 8 wks - 50/50 2221 7X9LPDW1905 0 0 4.47 0.29 4.69 0.18
WRFL - 23/50BI - Air
B7 New 2249 VN73WM00105 0 0 3.97 0.29 3.49 0.49
B7 Oven - 65C - 8 wks - 50/50 2234 VN73WM00105 0 0 6.64 0.22 7.54 0.27
B8 New 2286 0BURB411606 0 0 4.04 0.25 3.98 0.48
B8 Oven - 65C - 3 wks - 50/50 2289 0BURB411606 0 0 6.31 0.42 5.98 0.54
WRFL - 2/50BI - Air
B8 Oven - 65C - 5 wks - 50/50 2290 0BURB411606 0 0 6.16 0.34 6.68 0.97
WRFL - 2/50BI - Air
B9 New 2517 7XW8P7M1806 0 0 2.99 0.22 2.95 0.34
B9 Oven - 65C - 3 wks - 50/50 2520 7XW8P7M1806 0 0 4.72 0.11 4.68 0.32
WRFL - 2/50BI - Air
B9 Oven - 65C - 5 wks - 50/50 2521 7XW8P7M1806 0 0 4.88 0.15 4.62 0.29
WRFL - 2/50BI - Air
C New 1542 M6URFJ2R4802 0 0 2.87 0.12 3.33 0.16
C Phoenix 0309 M6URFJ2R1901 1.81 11897 3.04 0.29
C Phoenix 0311 M6URFJ2R417 5.45 43135 3.51 0.25
86
C LTDE - 60 mph - 100 hrs 1574 M6URFJ2R4802 0 0 2.98 0.22
C LTDE - 60 mph - 292 hrs 1559 M6URFJ2R4802 0 0 3.37 0.14 Failed LTDE @ 292 hrs
- BdTuCr
C Oven - 55C - 12 wks - 50/50 1581 M6URFJ2R4802 0 0 3.79 0.51 4.38 0.21
Capped
Capped
Capped - 24/75BI - 50/50
C P-END - 240 hrs 1557 M6URFJ2R4802 0 0 3.08 0.13
C3 New 2444 A30846JB1505 0 0 3.91 0.28 3.48 0.1
C3 Oven - 65C - 8 wks - 50/50 2452 A30846JB1505 0 0 4.67 0.28 4.58 0.32
C5 New 2487 ACUR3K42005 0 0 4.79 0.58 4.19 0.14
C5 Oven - 65C - 8 wks - 50/50 2491 ACUR3K42005 0 0 4.63 0.16 4.7 0.28
C7 New 2542 A3T645RW2206 0 0 2.71 0.12 2.72 0.15
C7 Oven - 65C - 3 wks - 50/50 2545 A3T645RW2206 0 0 5.91 0.37 5.16 0.47
WRFL - 2/50BI - Air
C7 Oven - 65C - 5 wks - 50/50 2546 A3T645RW2206 0 0 4.68 0.27 4.32 0.42
WRFL - 2/50BI - Air
C8 New 2567 P5UR4421806 0 0 3.53 0.18 3.59 0.21
C8 Oven - 65C - 3 wks - 50/50 2570 P5UR4421806 0 0 6.07 0.46 6.29 0.24
WRFL - 2/50BI - Air
C8 Oven - 65C - 5 wks - 50/50 2571 P5UR4421806 0 0 4.47 0.41 4.7 0.09
WRFL - 2/50BI - Air
D New 1142 B3DD462X2903 0 0 2.45 0.16 2.91 0.09
D Phoenix 0108 B3DDBDUX3201 1.58 23381 3.05 0.29 3.29 0.13
D Phoenix 0077 B3DD570X199 3.87 31396 2.44 0.16 2.74 0.15
D LTDE - 60 mph - 100 hrs 1174 B3DD462X2903 0 0 2.47 0.22
D LTDE - 60 mph - 508 hrs 1160 B3DD462X2903 0 0 2.5 0.05 Failed LTDE @ 377.35
hrs - ILS/BdD/TAL
D Oven - 55C - 12 wks - 50/50 1181 B3DD472X2003 0 0 3 0.22 3.04 0.11
Capped
D Oven - 65C - 8 wks - 50/50 1176 B3DD472X2003 0 0 2.5 0.18 3.38 0.15
Capped
D Oven - 65C - 8 wks - 50/50 1186 B3DD472X2003 0 0 2.86 0.29 3.22 0.25
Capped - 24/75BI - 50/50
D P-END - 096 hrs 1115 B3DD462X2903 0 0 2.22 0.03
D2 New 2371 PJC6XTLR2505 0 0 2.81 0.22 3.25 0.28
87
D2 Oven - 65C - 8 wks - 50/50 2374 PJC6XTLR2405 0 0 2.84 0.56 2.72 0.19
D3 New 2387 U9URTT93105 0 0 3.05 0.14 3.44 0.27
D3 Oven - 65C - 8 wks - 50/50 2386 U9URTT93105 0 0 3.26 0.28 4.61 0.2
D4 New 2430 3D40B8W1505 0 0 2.78 0.22 2.98 0.08
D4 Oven - 65C - 8 wks - 50/50 2425 3D40B8W1505 0 0 4.38 0.14 4.45 0.71
D5 New 2412 UPW8XDJ0805 0 0 3.38 0.14 3.95 0.24
D5 Oven - 65C - 8 wks - 50/50 2413 UPW8XDJ0805 0 0 4.38 0.31 Failed in oven at week 7
WRFL - 23/50BI - Air due to: Shoulder crack
ing
E New 1372 VN73WMB0302 0 0 4.07 0.33
E New 1319 VN73WMB0502 0 0 4.67 0.27
E Phoenix 0200 VN73WMB3502 0.53 5554 3.51 0.24
E Phoenix 0210 VN73WMA150 2.91 40594 4.87 0.23 3.93 0.4
E Phoenix 0201 W273WMB499 3.27 5.18 0.6
E LTDE - 60 mph - 100 hrs 1325 VN73WMB0902 0 0 4.16 0.21
E LTDE - 60 mph - 500 hrs 1654 VN73WM03205 0 0 6.69 0.6
E Oven - 55C - 12 wks - 50/50 1383 VN73WMB0702 0 0 6.06 0.23 5.61 0.68
Capped
E Oven - 65C - 8 wks - 50/50 1394 VN73WMB1402 0 0 6.29 0.33 4.65 0.13
Capped - 24/75BI - 50/50
E P-END - 168 hrs 1373 VN73WMB0502 0 0 4.47 0.07
G2 New 2126 PJ0RY5HV3305 0 0 2.1 0.15 1.88 0.07
G2 Oven - 65C - 8 wks - 50/50 2119 PJ0RY5HV3205 0 0 3.79 0.4 3.21 0.18
WRFL
G2 Oven - 65C - 8 wks - 50/50 2122 PJ0RY5HV3305 0 0 2.94 0.1 2.02 0.14 Failed in oven at week 1
WRFL - 23/50BI - Air due to: Turn-up blowout
at bead
H New 1242 PJ11FKKV4403 0 0 1.97 0.19 2.12 0.15
H Phoenix 0145 PJ11FKKV4501 1.36 15411 2.78 0.23
H Phoenix 0167 PJ11FKKV1201 1.99 42669 3.15 0.3 2.82 0.17
H Phoenix 0146 PJ11FKKV1300 2.99 64062 3.48 0.19
H Phoenix 0147 PJ11FKKV147 5.96 51053 2.99 0.33
H LTDE - 60 mph - 100 hrs 1266 PJ11FKKV4403 0 0 3.14 0.42
H LTDE - 60 mph - 100 hrs 1258 PJ11FKKV4403 0 0 2.75 0.34 Failed LTDE @ 100 hrs
- BdD
H LTDE - 60 mph - 100 hrs 1263 PJ11FKKV4403 0 0 2.87 0.25
H LTDE - 60 mph - 292 hrs 1259 PJ11FKKV4403 0 0 3.51 0.11 Failed LTDE @ 268.45
88
hrs
H Oven - 55C - 12 wks - 50/50 1281 PJ11FKKV4403 0 0 2.94 0.14 2.98 0.22
Capped
Capped
Capped - 24/75BI - 50/50
H3 New 2592 T7XD5JNH4905 0 0 3.81 0.15 4.08 0.19
H3 Oven - 65C - 3 wks - 50/50 2595 T7XD5JNH4905 0 0 5.46 0.27 3.63 0.49
WRFL - 2/50BI - Air
H3 Oven - 65C - 5 wks - 50/50 2596 T7XD5JNH4905 0 0 5.17 0.53 4.57 0.43
WRFL - 2/50BI - Air
L New 1442 A33X3HB3003 0 0 3.1 0.21 3.26 0.1
L Phoenix 0275 A33X3HB0702 1.06 10992 3.39 0.14 3.12 0.2
L Phoenix 0261 A33X3HB4901 1.24 22051 3.57 0.22
L Phoenix 0262 A33X3HB3100 2.65 54125 4.11 0.22
L LTDE - 60 mph - 100 hrs 1474 A33X3HB3003 0 0 4.51 0.46
L LTDE - 60 mph - 500 hrs 1424 A33X3HB0304 0 0 4.52 0.24 Tire failed @ 412 hrs -
Bead Torn into Sidewall
L Oven - 55C - 12 wks - 50/50 1481 A33X3HB3003 0 0 4.78 0.35 4.09 0.26
Capped
L Oven - 65C - 8 wks - 50/50 1476 A33X3HB3003 0 0 5.08 0.19 4.57 0.16
Capped
L Oven - 65C - 8 wks - 50/50 1486 A33X3HB3003 0 0 4.84 0.21 5.3 0.76
Capped - 24/75BI - 50/50
L P-END - 240 hrs 1457 A33X3HB3003 0 0 4.2 0.2 Tire failed @ 240 hrs -
Bead turn up sep, liner
sep
M10 New 2617 B72K2EHX1106 0 0 3.27 0.12 2.95 0.3
M10 Oven - 65C - 3 wks - 50/50 2620 B72K2EHX1106 0 0 3.53 0.28 3.64 0.31
WRFL - 2/50BI - Air
M10 Oven - 65C - 5 wks - 50/50 2621 B72K2EHX1106 0 0 3.82 0.31 4.07 0.65
WRFL - 2/50BI - Air
O1 New 2337 PJ0RH6LV3305 0 0 2.3 0.22 2.19 0.16
O1 Oven - 65C - 8 wks - 50/50 2334 PJ0RH6LV3305 0 0 3.06 0.18 2.56 0.1 Failed in oven at week 2
WRFL - 23/50BI - Air due to: Sidewall blo
wout
O2 New 2344 PJW8KDKV3405 0 0 2.22 0.27 2.44 0.1
O2 Oven - 65C - 8 wks - 50/50 2348 PJW8JLLV3405 0 0 3.41 0.13 2.95 0.07
O3 New 2324 UPURTX33205 0 0 2.79 0.13 3.08 0.24
O3 Oven - 65C - 8 wks - 50/50 2321 UPURTX33305 0 0 4.17 0.11 4.41 0.25
O5 New 2312 U9C6HTE3305 0 0 2.54 0.06 3.94 0.37
89
O5 Oven - 65C - 8 wks - 50/50 2308 U9C6HTE3305 0 0 3.44 0.17 4.44 0.29
P1 New 2013 UT73B9J2705 0 0 2.71 0.12 3.24 0.21
P2 New 2028 UP0RPAL2005 0 0 2.92 0.37 3.35 0.17
P2 Oven - 65C - 8 wks - 50/50 2035 UP0RPAL2005 0 0 4.18 0.19 4.28 0.42
P3 New 2018 UTHLPAN3205 0 0 2.81 0.16 3.12 0.13
P3 Oven - 65C - 8 wks - 50/50 2022 UTHLPAN3205 0 0 4.17 0.28 5.37 0.17
P3 New 2056 UTHLPAN2806 0 0 3.84 0.21 3.38 0.12
WRFL - 2/50BI - Air
WRFL - 2/50BI - Air
R2 Oven - 65C - 8 wks - 50/50 2134 XLW8E4231603 0 0 3.18 0.16 3.6 0.28 Failed in oven at week 8
WRFL - 23/50BI - Air due to: Sidewall blister
S1 New 2642 V4A64MCR5005 0 0 4.3 0.44 6.24 0.16
S1 Oven - 65C - 3 wks - 50/50 2649 V4A64MCR5005 0 0 6.31 0.41 8.91 0.22
WRFL - 2/50BI - Air
S1 Oven - 65C - 5 wks - 50/50 2646 V4A64MCR5005 0 0 6.54 0.21 9.81 0.16
WRFL - 2/50BI - Air
T2 New 2667 9TKU93A0706 0 0 2.95 0.29 3.24 0.11
T2 Oven - 65C - 3 wks - 50/50 2670 9TKU93A0706 0 0 4.19 0.22 3.5 0.12
WRFL - 2/50BI - Air
T2 Oven - 65C - 5 wks - 50/50 2671 9TKU93A0706 0 0 3.36 0.3 3.44 0.16
WRFL - 2/50BI - Air
U2 New 2081 EUFC3TMR4705 0 0 4.28 0.01 4.85 0.38 Run Flat Tire
U2 Oven - 65C - 3 wks - 50/50 2084 EUFC3TMR4705 0 0 5.26 0.19 7.16 0.6 Run Flat Tire
WRFL - 2/50BI - Air
U2 Oven - 65C - 5 wks - 50/50 2085 EUFC3TMR4705 0 0 5.9 0.11 7.38 0.3 Run Flat Tire
WRFL - 2/50BI - Air
90
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93
DOT HS 811 296

March 2010

Test - 45654414 - Rubber

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DOT HS 811 296 March 2010

NHTSA Tire Aging Test

This publication is distributed by the U.S. Department of Transportation, National

7. Author(s) 8. Performing Organization Report No.

Akron, Ohio 44305 DTNH22-03-D-08660,

Washington, D.C. 20590

In-Service (Field) Tires

Oven Aged Tires

Wheel-Tested (LTDE and P-END) Tires

Fourier Transform Infrared Spectroscopy (FTIR)

Figure 1. FTIR Test

Energy Dispersive X-ray Spectroscopy (EDAX)

Figure 2. SEM/EDAX Test

X-ray Fluorescence (XRF)

Figure 3. XRF Test

Pyrolysis-Gas Chromatography/Flame Ionization Detector (GC/FID)

Figure 4. Pyrolysis GC/FID Test

Pyrolysis-Gas Chromatography/Mass Spectroscopy (GC/MS)

Thermal Gravimetric Analysis (TGA)

Figure 5. TGA Test

Figure 6. Extraction Test

Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-AES)

Figure 7. ICP-AES Test

Pump Starting Test

Oxygen Content (Fixed Oxygen by Weight)

Figure 8. Permeability Test

Figure 10. Modulus Profiling Test

Probe Probe in Contact with Sample

ASTM D 2240 Type A Durometer Hardness

INNERLINER FORMULA RECONSTRUCTION

Table 1. Model Innerliner Formulation

Ingredient phr % by weight

Table 2. Analyses Used in Formula Reconstruction Estimates for Innerliner Compounds

Beilstein test. Presence of chlorine or bromine identi­

Part I - Model Liner Compound Chemical Analysis

Table 3. Model Bromobutyl/Natural Rubber Liner Compounds

Table 4. Model Chlorobutyl/Natural Rubber Liner Compounds

Table 5. Model Bromobutyl/SBR Liner Compounds

Table 6. Six Additional Model Compounds for Liner Permeability Testing

Acetone Extraction of Model Liner Compounds

Table 7. Acetone Extraction of Model Liner Compounds

Oxygen Content of Model Liner Compounds

Table 8. Oxygen Content of Model Liner Compounds

ICP-AES of Model Liner Compounds

Table 9. Ash Composition of Model Liner Compounds

TGA of Model Liner Compounds

Figure 11. Overlay Plot of the TGA Weight Loss Curves

Figure 12. Overlay Plot of the TGA Derivative Curves

Table 11. Actual Compositional Analysis (wt%)

FTIR of Model Liner Compounds

Table 12. FTIR Analysis

Compound Polymer Identification

Figure 17. FTIR of Model Liner Compounds 1, 3, 5, 7, 9

Wave Number (cm-1) Wave Number (cm-1)

Wave Number (cm-1)

XRF Analysis of Model Liner Compounds

Table 13. XRF Analysis Results of Model Compounds

Barcode Bromine Chlorine Sulfur Calcium Iron Potassium Zinc

EDAX of Model Liner Compounds

Table 14. EDAX of Model Compounds

Liner 1 Liner 3 Liner 5 Liner 7 Liner 9

Figure 20. Correlation between Bromine Intensity and phr Bromobutyl

Bromine Intensity (c/s)

Beilstein test. Presence of chlorine or bromine identi

UT Futura [Pep Mi Mi