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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
Figure 36. Permeability of Model Compounds at 70°C as a Function of Butyl Content ............. 51
Figure 37. Permeability of Model Compounds at 21°C as a Function of Butyl Content ............. 53
iii
Figure 38. Permeability of Model Compounds at 65°C as a Function of Butyl Content ............. 53
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
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:
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.
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%.
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.
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).
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.
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.
10
• 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
12
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
13
were used later in this report to more precisely characterize the compositions of liners extracted
from tires.
14
15
16
17
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.
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)
-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%)
Compound Liner 1 Liner 3 Liner 5 Liner 7 Liner 9
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
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
Derivative (wt%/min)
-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
Derivative (wt%/min)
-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
Derivative (wt%/min)
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
22
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
Liner #9
100
90
80
Transmission (%)
70
60
50
40
30
20
10
4000 3600 3200 2800 2400 2000 1600 1200 800 400
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.
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)
25
40
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 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
27
Table 18. TGA Compositional Analysis of the Six Phoenix Tire Models (wt%)
Tire Number 1030 1132 1227 1337 1427 1530
NHTSA Tire Type B D H E L C
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
28
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
31
32
33
34
35
36
37
38
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
39
Polyisoprene (gm)
R2 = 9.556E-01
0.2
0.0
0 200000 400000 600000 800000 1000000
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
0.350
0.200
0.150
0.100
0.050
0.000
0 50000 100000 150000 200000 250000
Butadiene Peak Area (uV*sec)
41
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.
0.12
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
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
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
44
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
0.08
Styrene Butadine Polymer (mg)
0.04
0.02
0.00
0.E+00 2.E+08 4.E+08
Styrene Peak Area (uV*sec)
45
0.045
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
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
48
49
50
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)
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
7.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)
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
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
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
8.0E-08
Permeability (cm 2 /sec-atm)
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
7.0E-07
Permeability (cm 2 /sec-atm)
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
60
61
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)
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
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
Table 46. Average Change in Indentation Modulus of Shoulder Region Innerliner 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 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
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
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
Table 49. Average Change in Indentation Modulus of Shoulder Region Innerliner 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
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
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
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
Weeks Oven Aging @ 65�C with 23-hour Break-in
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
Weeks Oven Aging @ 65�C with 2-hour Break-in
76
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
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
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
Weeks Oven Aging @ 65�C with 23-hour Break-in
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
Weeks Oven Aging @ 65�C with 2-hour Break-in
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
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
Oven - 65C - 8 wks 2.91 0.36 MPa/wk 1.05 0.13 MPa/wk
- 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
Oven - 65C - 5 wks 1.45 0.29 MPa/wk 1.87 0.37 MPa/wk
- 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
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 LTDE - 60 mph - 100 hrs 1058 APC6BB113803 0 0 2.94 0.19
B LTDE - 60 mph - 292 hrs 1080 APC6BB113803 0 0 2.86 0.19
B LTDE - 60 mph - 292 hrs 1059 APC6BB113803 0 0 4.53 0.44
B LTDE - 60 mph - 508 hrs 1084 APC6BB113803 0 0 3.12 0.13
B LTDE - 60 mph - 508 hrs 1060 APC6BB113803 0 0 4.68 0.35
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
WRFL - 23/50BI - Air
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
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)
C LTDE - 60 mph - 100 hrs 1574 M6URFJ2R4802 0 0 2.98 0.22
C LTDE - 60 mph - 292 hrs 1579 M6URFJ2R4802 0 0 3.48 0.29
C LTDE - 60 mph - 292 hrs 1559 M6URFJ2R4802 0 0 3.37 0.14 Failed LTDE @ 292 hrs
- BdTuCr
C LTDE - 60 mph - 508 hrs 1584 M6URFJ2R4802 0 0 3.84 0.31
C Oven - 55C - 12 wks - 50/50 1581 M6URFJ2R4802 0 0 3.79 0.51 4.38 0.21
Capped
C Oven - 65C - 8 wks - 50/50 1576 M6URFJ2R4802 0 0 4.38 0.26 4.14 0.52
Capped
C Oven - 65C - 8 wks - 50/50 1586 M6URFJ2R4802 0 0 4.62 0.61 4.62 0.41
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
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
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 - 100 hrs 1158 B3DD462X2903 0 0 2.63 0.09
D LTDE - 60 mph - 292 hrs 1159 B3DD462X2903 0 0 2.27 0.03
D LTDE - 60 mph - 292 hrs 1179 B3DD472X2003 0 0 2.65 0.44
D LTDE - 60 mph - 508 hrs 1160 B3DD462X2903 0 0 2.5 0.05 Failed LTDE @ 377.35
hrs - ILS/BdD/TAL
D LTDE - 60 mph - 508 hrs 1184 B3DD472X2003 0 0 2.56 0.19
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
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)
D2 Oven - 65C - 8 wks - 50/50 2374 PJC6XTLR2405 0 0 2.84 0.56 2.72 0.19
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
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 - 100 hrs 1330 VN73WMB4002 0 0 4.22 0.06
E LTDE - 60 mph - 292 hrs 1338 VN73WMB4002 0 0 5.62 0.16
E LTDE - 60 mph - 292 hrs 1366 VN73WMB1602 0 0 4.88 0.18
E LTDE - 60 mph - 500 hrs 1654 VN73WM03205 0 0 6.69 0.6
E LTDE - 60 mph - 508 hrs 1311 VN73WMB4002 0 0 5.5 0.41
E LTDE - 60 mph - 508 hrs 1354 VN73WMB4002 0 0 6.35 0.15
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
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)
hrs
H Oven - 55C - 12 wks - 50/50 1281 PJ11FKKV4403 0 0 2.94 0.14 2.98 0.22
Capped
H Oven - 65C - 8 wks - 50/50 1276 PJ11FKKV4403 0 0 3.5 0.22 2.97 0.37
Capped
H Oven - 65C - 8 wks - 50/50 1286 PJ11FKKV4403 0 0 3.17 0.14 3.68 0.35
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 - 292 hrs 1480 A33X3HB3003 0 0 3.68 0.13
L LTDE - 60 mph - 292 hrs 1459 A33X3HB3003 0 0 4.08 0.36
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
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
O5 New 2312 U9C6HTE3305 0 0 2.54 0.06 3.94 0.37
89
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)
O5 Oven - 65C - 8 wks - 50/50 2308 U9C6HTE3305 0 0 3.44 0.17 4.44 0.29
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
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
WRFL - 23/50BI - Air
P3 New 2056 UTHLPAN2806 0 0 3.84 0.21 3.38 0.12
P3 Oven - 65C - 3 wks - 50/50 2059 UTHLPAN2806 0 0 4.39 0.28 4.63 0.39
WRFL - 2/50BI - Air
P3 Oven - 65C - 5 wks - 50/50 2060 UTHLPAN2806 0 0 4.77 0.23 6.02 0.62
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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