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CORRELATION OF LOCALLY-BASED PERFORMANCE OF ASPHALTS
WITH THEIR PHYSICOCHEMICAL PARAMETERS
TASK 1 REPORT JANUARY 1988
IOWA DOT PROJECT HR-298 ERI PROJECT 1942
Sponsored by the Highway Division of the Iowa Department of Transporatation and the
Iowa Highway Research Board.
ENGINEERING RESEARCH INSTITUTE
iowa state university eri 88-408
CORRELATION OF LOCALLY-BASED PERFORMANCE OF ASPHALTS .
WITH THEIR PHYSICQCHEMICAL PARAMETERS
TASK 1 REPORT JANUARY 1988
D. Y. LEE B.V.ENUSTUN
IOWA DOT PROJECT HR-298 ERi PROJECT 1942
Sponsored by the Highway Division of the Iowa Department of Transportation and the
Iowa Highway Research Board.
"The opinions, findings, and conclusions expressed in this publication are those of the authors and not necessarily those of the Highway Division of the Iowa Department of Transportation."
1.
2.
INTRODUCTION
1.1. Background 1.2. Objectives 1.3. Program of Study
EXPERIMENTAL
2.1. Materials 2.2. Procedures
iii
TABLE OF CONTENTS
2.2.1. Rheological properties 2.2.2. HPLC 2.2.3. Thermal analyses 2.2.4. X-ray diffraction
3. RESULTS
3.1. Rheological Properties 3.2. HPLC 3.3. Thermal Analyses 3.4. X-ray Analyses 3.5. Correlations
3.5.1. Rheological properties 3. 5 • 2 • . HP-GPC 3.5.3. Thermal analyses 3.5.4. X-ray diffraction
4. SUMMARY AND CONCLUSIONS
5. RESEARCH PLAN FOR TASK 2 (YEAR 2)
6. ACKNOWLEDGMENTS
7. REFERENCES
APPENDIX I
APPENDIX II
APPENDIX III
Page
1
1 2 3
3
3 5
5 11 16 21
22
22 43 43 48 48
53 53 57 57
58
59
60
61
iv
LIST OF TABLES
Table 1. Rheological properties.
Table 2. Temperature susceptibility.
Table 3. Low-temperature cracking properties.
Table 4. Thin film oven test hardening.
Table 5. Properties of recovered asphalts.
Table 6. Viscoelastic properties of thermal cycled samples at +5°C.
Table 7. Results of HP-GPC analyses.
Table 8. DSC test results.
Table 9. Shoulder height of x-ray diffraction spectrum at 28 = 4.83°C.
Page
23
29
36
38
42
46
47
49
50
v
LIST OF FIGURES
Figure 1. Summary of proposed research.
Figure 2. Modified cone and plate viscometer.
Figure 3. Mechanical model corresponding to asphalts at a low temperature.
Figure 4. Viscometer rotation plotted vs time (sample: JOS-01-0 at +S°C, after cooling from +2S°C for 6S hrs; L = 100 g;
Page
4
8
9
cone constant = 121S p. deg/g. sec. 10
Figure S. HP-GPC units. 13
Figure 6. (a) (b) (c)
DSC thermogram of B297S at 2 deg/min scanning rate. -18 DSC thermogram of B297S at S deg/min scanning rate. -19 DSC thermogram of B297S at 10 deg/min scanning rate.-20
Figure 7. Cross-section of x-ray analysis sample holder.
Figure 8. Penetration at 2S°C (77°F) and at S°C (41°F).
Figure 9. Viscosity at 60°C (140°F).
Figure 10. Viscosity at 13S°C (27S°F).
Figure 11. Ring and ball softening point.
Figure 12. BTDC of original (O} Jebro asphalts.
Figure 13. BTDC of original (0) Koch asphalts.
Figure 14. Penetration index.
Figure lS. PVN at 60°C (140°F).
Figure 16. PVN at 13S°C (27S°F).
Figure 17. Viscosity temperature susceptibility.
Figure 18. Retained penetration and viscosity ratio, thin film oven test.
Figure 19. PVN vs viscosity ratio.
22
24
2S
26
27
30
31
32
33
34
3S
39
40
vi
LIST OF FIGURES (Cont'd.)
Figure 20. Relationships between viscosity at 140°F (60°C) in poises, penetration at 77°F (25°C), and temperature susceptibility. 41
Figure 21. Viscoelastic properties of JOS-01-0, Jl0-01-0 and J20-01-0 at +s 0 c. 44
Figure 22. Viscoelastic properties of SC-SU and WR-SU at +S°C. 45
Figure 23. (LMS) 18 •125 plotted vs LMS. S6
1
I. INTRODUCTION
1.1. Background
Current specifications for asphalt cement contain limits on physical .·
properties based on correlations established in the past with field performance
of asphalt pavements. Recently, however, concerns have arisen that although
current asphalts in use meet these specifications, they are not consistently
providing the long service life once achieved.
There are a number of logically possible explanations of this situation:
[1] A considerable concern is associated with the recent world crude oil supply
and the economic climate after the 1973 oil embargo which may have affected the
properties of asphalt of certain origin (Hodgson, 1984). Blending several
crudes, as routinely practiced in refineries to produce asphalts meeting current
specifications, may have upset certain delicate balances of compatibility
between various asphaltic constitutents, which may manifest itself in their
long-term field performance bu~ not in original physical properties specified in
the specifications (Goodrich et al., 1985; and Petersen, 1984).
[2] The increased volume and loads of traffic on highways, which have occurred
over the decades, may have shortened the life span of pavements, indicating the
necessity of revising specification limits and/or imposing new provisions to
maintain desired durability.
[3] Inadequate mixture design, particularly poor gradation of aggregates,
changing construction practices and improper use of additives may also be
responsible for early deterioration of asphalt pavements (Anderson and Dukatz,
1985; and Hodgson, 1984).
[4] Specifications based only on physical properties of asphalts do not
guarantee adequate performance.
2
While the performance of the asphalt pavements could be improved by
judicious application of improved mix design techniques, more rational thickness
design procedures, better construction methods and quality control measures,
selection of asphalts based on performance-related properties, tests, and
specifications is the key to durable asphalt pavements.
Highway Research Project HR-298 was approved by the Iowa Highway Research
Board on December 2, 1986 to study the relationships between the performance of
locally available asphalts and_their physicochemical properties under Iowa
conditions with the ultimate objective of development of locally ·and
performance-based asphalt specifications for durable pavements; funding for Task
1 (year 1) of the three-year study was authorized in January 1987. This Task 1
report describes work performed and findings resulted during the first year of
the study •
..!..:!:_ Objectives
The objective of this study was to establish locally-based quality and
performance criteria for asphalts, and ultimately to develop performance-related
specifications ·based on simple physicochemical methods. Three of the most
promising chemical methods (high p~rformance liquid chromatography or HPLC,
thermal analysis or TA and X-ray diffraction or XRD) were selected to analyze
samples of:
a. Virgin asphalts from local suppliers.
b. Virgin asphalts subjected to thin film oven test.
c. Asphalts extracted from laboratory mixes prepared using the virgin
asphalts after they are artifically aged in chambers under
accelerated environmental conditions (exposures to ultraviolet
and infrared radiations, temperature and moisture extremes).
d. Asphalts extracted from pavements with known performance records.
;
.·•
3
The results obtained will be analyzed to find the fundamental asphalt
property variables (such as viscosity, molecular size, micelle size, transition
temperatures, temperature susceptibility, resistance to oxidative hardening,
reactivity with environment, etc.) which directly affect the field performance
in Iowa.
On the basis of the laboratory-field-property-performance correlations, we
expect to formulate specifications and establish testing procedures which can be
performed in the transportation materials laboratories of the Iowa DOT and ISU.
1.3. Program of Study
The ultimate objective of this study is to establish locally-based quality
and performance criteria as a basis for asphalt specifications, in other words,
the development of performance-based specifications for the state of Iowa.
This research will be carried out in six tasks completed in three years.
The specific tasks to be performed were presented in the research proposal and
are shown iri Figure 1.
2. EXPERIMENTAL
2.1 Materials
Asphalt cement samples representing those commonly used in Iowa were
obtained from Koch Asphalt Co., St. Paul and Jebro, Inc., Sioux City, Iowa. Two
sets of asphalt samples were supplied by each of the two suppliers: each set of
samples consisted of one AC-5, one AC-10 and one AC-20. The two sets of samples
from Jebro were received in February and September 1987; those obtained from
Koch were received in June and October 1987. A total of 12 virgin asphalt
cement samples were tested in Task 1. They were identified as J0501, J0502,
JlOOl, J1002, J2001, J2002, K0501, K0502, KlOOl, K1002, K2001 and K2002.
/
SELECT & .. .• OBTAIN ....,
r-. ASPHALT -CEMENTS .. THIN - FILM -- OVEN TESTS
TASK 1 TASK 1 ...
,, 1 • ,,,.
"' ...., .... -, SELECT & PREPARE MIXES
, ....,. TEST.
OBTAIN TEST MIXES EXTRACT ASPHALT ~ ~ - CEMENTS AGGREGATES - ASPH!!LTS --. .... .. .. - TASK 2 TASKS 2 & 3 TASKS 2 & 3
TASKS 1, 2, & 3 TASK 2 ...
+ j~ j~ .. ,
"' r ..... ARTIFICIALLY 1 ~
AGE MIXES , SELECT &
. .p.
SAMPLE -PAVEMENTS ... TASK 2 .. PERFORMANCE
CORRELATICN .
TASK 3· -j ~
... TASK 4
I • , .... .... / .... / .... , OBTAIN MATERIAL,
OBTAIN OBTAIN CONSTRUCTION, PREPARE PREDICT ORIGINAL ORIGINAL QUALITY CONTROL, ASPHALT PAVEMENT ' -
AGGREGATES ASPHALTS . MlUNTENANCE, SPECIFICATIONS - PERFORMANCE . PERFORMANCE & TRAFFIC DATA ' TASK 3 TASK 3 TASK 6 TASK 5 TASK 3
' -.
FIGURE l . SUMMARY OF PROPOSED RESEARCH
5
In addition, two sets of asphalt samples recovered from pavement cores
taken in April 1987°were provided by the Materials Laboratory, Iowa DOT. These
samples were taken from seven-year old pavements of known performance with
respect to cracking (Marks and Huisman, 1985). They were identified as Sugar
Creek (surface, binder and base) and Wood River (surface, binder and base),
respectively.
Furthermore, 25 reference asphalt samples with extensive data from FHWA and
a reference asphalt from Montana State University were also obtained and will be
evaluated in Tasks 4 to 6.
2.2. Procedures
The 12 virgin asphalts (0 samples) were first aged following thin-film oven
test procedure (ASTM D 1754) and identified as R samples. The 12 original (0)
. and 12 aged (R) samples were then characterized by physical and chemical tests
as described in the following sections:
2.2.1. Rheological properties : Penetration at 41 and 77°F, viscosity at 77, 140
and 275°F, and ring-and-ball softening point tests were performed on both
original and TFOT aged residue asphalts. From these data penetration index
(PI), pen-vis number (PVN), viscosity temperature susceptibility, cracking
temperature, critical stiffness and critical stiffness temperature were
calculated.
In addition to the above mentioned standard tests, certain rheological
properties of a few samples were studied in greater depth at a moderately low
temperature, which might have some bearing on their low temperature performance
in the field. They were the samples JOS-01-0, Jl0-01-0, J20-0l-O, SC-S (Sugar
Creek surface) and WR-S (Wood River surface). The primary purpose of these
experiments was to see how the low temperature transformations revealed by
thermal analysis, to be described later, reflect on rheological properties.
6
The secondary purpose was to study the time dependence of these properties at a
low temperature.
A review of the relevant literature reveals that a considerable effort has
been made by the researchers sponsored by asphalt producers to establish a
universal relationship to describe rheological properties of all asphalts
(Brodnyan et al., 1960; Sisko and Brunstrun, 1968; Jongepiev and Kuilman, 1969;
and Dobson, 1969). However, ·the quest'ion of how fast an asphalt sample acquires
these properties when brought to a given temperature from a different
temperature, or whether these properties are indeed single valued functions of
temperature for practical purposes, seems to have received little attention.
The lower the temperature, the more valid become these questions due to sluggish
behavior of asphalts. The'contributions of many authors in this field were
confined to their in-passing remarks that rheological properties of asphalts
depend on their thermal history.
Hoping to get some discriminating information on asphalts possibly related
to thermal cracking of pavements, we studied viscoelastic properties of a few
samples at +S°C as a function of their thermal history and time. The reasons
for choosing this temperature were the following:
(1) It was the lowest temperature at which rheological tests were
manageable with the equipment on hand.
(2) It may reasonably be considered as an intermediate winter temperature
which prevails after a warm spell or after a severe cold.
(3) It is within a temperature range in which most·asphalts suffer a
thermal (endothermic) transformation upon heating (Noel and Corbett, 1970;
Albert et al., 198S; and Brule et al., 1986).
Experiments were designed to estimate the elastic shear modulus of the samples,
as well as their Newtonian viscosities at +S°C, using a cone and plate
viscometer.
7
To provide Newtonian conditions, the samples had to be sheared at extremely
low rates. This requirement coupled with shortening the testing time made it
necessary to increase the accuracy of displacement measurements by two orders of
magnitude. This was achieved by an optical method of measurement of the
rotation of the cone. For this purpose a replaceable reflecting mirror was
fastened on the cone axle as shown in Figure 2. A focusable beam of light from
a projection pointer was directed to the mirror, and its reflection on a
graduated screen was used to measure the rotation of the cone with an accuracy
of better than± 0.005 degree. With this modification of the cone and plate
-5 instrument, it was possible to work at an angular velocity of as low as 2 x 10
degree/sec.
An analysis of the experimental results has shown that the rheological
behavior of asphalts under Newtonian conditions at low temperatures can be
described reasonably well by the equation
x = Lt/8 + L(l - e-£1t/8l)/El + L(l - e-£2t/82)/£2
where x is the angle of rotation of the cone under an applied load L, t is
(1)
time; 8, 81 , 82 , £1 and Ez are constants. Equation (1) is known to describe the
motion of the viscoelastic system shown in Fig. 3 where the dashpots represent
Newtonian viscous elements and the springs represent Hookeian elastic elements
(Pagen, 1964). 8 characterizes the viscous behavior of the left-hand-side
dashpot, and is proportional to the true (steady) viscosity of the asphalt
sample. The proportionality constant is known as the "cone constant". 81 and 82
are similarly associated with the second and the third dashpots, respectively. £1
and £2 are the force constants of the first and the second springs,
respectively. They are proportional to the shear moduli of elasticity of the
sample. A typical plot of experimental x vs. t data is given in Fig. 4.
8
1·.
Figure 2. · Modified cone and plate vis.cometer.
9
/J,
,(J
L.
Figure 3. Mechanical model corresponding to asphalts at a low-temperature.
A detailed analysis of the experimental results shows, in general, that at
+5 °C , B ~ B1 > B2 and El < E2 •
The ref ore (2)
These make the third term in Eq. (1) negligible for most purposes.
An analytic examination of Eq. (1) in its exact form reveals that if
shearing continues long enough the experimental points on a x vs. t plot fall on
a straight line with a slope of L/ B, and an intercept of L ( l/q + l/E 2) as
indicated in Fig. 4. Therefore, it was possible to estimate the viscosity index B
and an equivalent shear modulus index £ defined by
1/ £' = l/E1 + l/Ez
from the slope and the intercept, respectively, of the experimental straight
line for a given set of data.
(3)
The viscoelastic properties of all five samples were investigated at +5°C
as a function of time by this method after mounting each sample on the cone and
plate assembly and keeping at 25°C for 24 hours.
I /.0 i-
0 500 /OOo
TIME
: j --~~-~.:__ __ :;---j
200()
Figure 4. Viscometer rotation plotted vs. time (Sample: JOS-01~0 at. +5°C, after cooling from +25°C for 65 hrs; L ~ lOQ g; cone constant= 1215 p. deg/g/sec).
11
Three of the samples (JOS-01-0, sc~s, and WR-S) were also investigated
0 similarly after quenching them from room temperature to -30 C for one hour and
rewarming to +5°C at a rate of 0.7 degrees/min. This conditioning was an
attempt to simulate the occasional severe winter conditions.
2.2.2. High performance liquid chromatography (HPLC): HPLC, specifically high
pressure gel permeation chromatography (HP-GPC) is a technique by which the
molecular size distribution of asphalt is determined by means of gels of
selected pore sizes as in sieve analysis. Recent reports from a Montana asphalt
quality study using this technique have shown considerable promise and have led
the Montana State Department of Highways to institute special provisions based
on requirements based on HP-GPC (Jennings et al., 1982, 1985, 1988). While
there were unresolved exceptions, it has been concluded that large molecular
size asphaltic constituents contribute to low temperature cracking of asphalt
pavements. Other studies (Zenewitz and Tran, 1987; and Button et al., 1983)
have related the amounts of small molecular size fractions to rutting and tender
mixtures~
Even though the purchase request for HPLC equipment was initiated in early
February 1987, shortly after the start of the research project, the equipment
was not complete and operational until late August 1987. While we were able to
complete the analyses of all the asphalt samples following the Montana protocol,
because of time limitations we were not able to explore other experimental
techniques and data analysis approaches. Recognizing the potential of the
HP-GPC technique and the weakness of the Montana procedure and interpretation,
it is planned that a more vigorous investigation for alternative procedures and
data interpretations of HP-GPC work will be pursued in Task 2.
A high performance gel permeation chromatography system (Waters) was used
during this study. This system consisted of a solvent reservoir; a high
pressure pump (Waters model 510); an injector (Waters model U6K); three
12
0 0 • .
"Ultrastyragel" columns (Waters),. one 1000 A.followed by two 500.A units;· a UV
absorbance. !fetec;tor set._ at ~40 nm. (Waters model 481); and .a data module (Waters
mqdel745) •. Th~ assembly of these units are seen in Fig. 5.
The solvent reservoir,-w~s. a one liter bott:le of tetrahydrofuran (THF) with
a stopper that had been modified so that three tubes entered the solvent "
reservoir.
HPLC grade THF is. packaged under nitrogen to preserve spectral integriq(
and is not inhibited for full .UV transparency. To preserve these co~d'itions and
isolate the THF from atmosphere, helium.gas was slowly bubbled into the solvent
via the tubing connected to the helium gas cylinder.
The second tube in the stopper contained desiccant chips to prevent
moisture from entering the solvent.
The third tube in the stopper was the draw-off line through which solvent
was drawn from the reservoir to the pump.
The dual head design~of the Waters Model 510 pump allowed one head to fill
with solvent while the other was delivering solvent at increased pressure to the
system and vice versa. This alternating action minimized flow fluctuations and
improved flow rate.
Asphalt samples of 0.02 to 0.05 grams were accurately weighed into a 20 ml.
glass Scintillation vial. THF (drawn from the solvent reservoir) was pipetted
into the vial to prepare a 0.5% (w/v) solution. The sample solution was then
transferred to a 15 ml. centrifuge tube, capped, and centrifuged.for 10 minutes
to remove foreign particles capable of plugging columns. Samples were weighed
ahead of time but dilution and centrifugation were done just before injection.
The delay time between sample dissolution and injection was kept constant from
sample to sample (approximately 30 minutes +5 minutes).·
Figure 5. HP-GPC units.
14
The Model U6K Universal Liquid Chromatograph Injector allowed samples to be
loaded at atmospheric pressure while THF was simultaneously being delivered to
the system at increased pressure. This was accomplished by isol?ting the sample
loading channel from the main stream while injecting a sample. The sample
channel, opened to atmosphere, made it possible to displace solvent with sample
as the sample was delivered from a syringe~ After sample injection, the channel
.was closed to atmosphere and pressurized. The solvent preferentially passed
through the sample channel (since it followed the path of least resistance) and
carried the sample to the columns. Flow rate was set at 0.9 ml./min. Sample
size was 100 ul.
The gel permeable columns separated the sample by molecular size. The
total solvent volume in the columns was distributed between interstitial volume
and pore volume. Each column contained six milliliters of interstitial and six
milliliters of pore volume for a total of twelve milliliters per column. Thus,
the system with three columns had a total of 36 milliliters of solvent volume.
Therefore, large molecules that didn't penetrate the pores (referred to as total
exclusion), passed directly through the columns and exited (or eluted) after 18
milliliters of interstitial solvent.
However, small molecules that penetrated all pores (total inclusion of both
interstitial and pore volumes) eluted after 36 milliliters of solvent.
Intermediate size molecules eluted between 18 and 36 milliliters. During the
method's development, columns of appropriate pore size were selected so that the
sample was neither totally excluded nor included, but distributed in the range
0 0
between 18 and 36 milliliters. A 1000 A and two 500 A columns in series
effectively separated the components in asphalt samples. To determine the
actual exclusion and inclusion pore sizes of the columns, prior to the present
studies a series of monodisperse polystyrene standards of known molecular
15
weight were analyzed using the uv detector at 254.nm. 'The following retention
times were determined from these standards:
Molecular Weight
470,000 240,000 110,000 35,000 8,500 1,800
Phenolphtalein (320) Xylene (106)
Retention Time (minutes)
17.20 17.34 17.58 18.32 20.61 23.79 28.50 34.98
These retention times will vary depending on the individual columns, the
precise flow rate, the amount of dead volume in the system and possible other
factors such as temperature and dilution time. Note that at molecular weights
greater than 110,000 there was little change in retention time, this indicated
total exclusion. The lower limit was not determined.
Gel particles within the columns are compressible and may be damaged at
high pressures so the maximum pump flow rate was set at 1.2 ml./min. (or 2000
psi backpressure). Additionally, column temperature fluctuations cause
particles to swell or shrink, thus changing pore size. To alleviate this
0 problem, a constant temperature water bath at 27 C isolated the columns from
room temperature fluctuations and maintained columns at a constant temperature.
The sample eluted from columns passed through the sample side of the flow
cell of the Lambda-Max Model 481 LC Spectrophotometer where a beam of UV light
passed through the sample. The amount of absorbed light is assumed to be
directly proportional to the concentration of asphaltic components. Absorption
units detected by spectrophotometer were converted to volts and transferred to
the Waters 745 Data Module where the signal was amplified and plotted versus
16
time. The resulting chromatograph depicted the molecular size distribution of
the sample. Chromatographs were automatically divided into slices of specified
time intervals and the area, molecular weight per slice, and cumulative percent
of area were calculated from dialog input and printed at the end of the
analysis. To standardize procedures, samples were analyzed using the same
dialog settings.
Twelve virgin asphalt (O) samples and their TFOT residues (R samples), as
well as six recovered core samples were analyzed by this method to determine
their large molecular size (LMS) ratings. This rating has been proposed by the
Montana State University research group as an index of low temperature
susceptibility of an asphalt sample (Jennings et al., 1980; 1982; and 1985). It
has been defined as the percent of the area under the chromatographic
(340 µm) UV absorbance vs. elution time curve as far as to a retention time (ca.
22 minutes) at which a standard asphalt sample exhibits its second inflexion
point, relative to the total surface area under the whole curve. Therefore,
prior or subsequent to each run, the standard asphalt supplied by the Montana
State University was also run to determine the correct cut-off time for that
sample. This way it was possible to make the estimations independent of
possible day-to-day drifts in the performance of the GPLC equipment. The
absorbance printouts of the data module were used for these computations.
Needless to add that between the runs, the "Ultrastyragel" columns were
routinely flushed with pure solvent for a sufficient length of time. The
columns were also flushed with pyridine once approximately in every two months.
2.2.3. Thermal analyses: Thermal analysis techniques have been used
extensively by chemists to identify and characterize polymers. Breen and
Stephens (1967) recommended the use of glass transition temperature from thermal
analysis data for predicting low temperature cracking of asphalt pavements and
also point out the possibility of using it for predicting cracks due to aging.
I
17
Following the methodologies initiated by Ferry et al. (Ferry, 1961) for
polymers, Schmidt et al. (1966) determined glass transition temperatures of
asphalts volumetrically and used them to predict their low temperature
viscosities. The predicted viscosities were not in good agreement with the
measured viscosities, in general. However, although based on a single
comparison, Schmidt (1966) correlates a high glass transition point, rather than
a high viscosity, to low temperature cracking of pavements.
The glass transition point is known to depend on the rate of temperature
change during scanning. Schmidt et al. recommend a rate of 2 degrees/min. to
obtain meaningful data. They tested 52 reference samples supplied by the Bureau
of Public Roads. In the present study we ran DSC tests in sealed aluminium
sample holders with one of these samples (B 2975, an AC-10 asphalt) at various
heating rates, using a DuPont 1090 instrument. The results are shown in Figs.
6a, b, and c. The glass transition point of this sample reported by Schmidt et
al. is tg = +S.4 c. Glass transitions. traceable on the curves by the method of
inflexion point (Wendlandt, 1984) in the vicinity of this value are indicated on
these figures. It appears from those values that the higher the heating rate,
the higher the estimated transition point, and that the tg estimated at a rate
of 5°C/min. is the closest to the reported value• We, therefore, used this rate
throughout the present work, scanning between -80 and +80°C. The precooling
0
rate was 10 C/min.
However, whether the apparent inflexion point in the vicinity of +5
observed with the sample B2975 indicates a glass transition or a transformation
of another kind is an open questi~n. Indeed these DSC thermograms are very
similar to those reported by Noel and Corbett (1970) and Albert et al. (1985).
The apparent inflexion point just mentioned happens to be in a region which is
interpreted by these authors as the region of an endothermic transformation such
as fusion or dissolution of crystallized asphaltic components, as will be
. Somplet B 2975 Sizes 11.4 MG I lB DEG/MIN CL Rale1 2 DEG/MIN W/ DEWAR Programs Inleraotive DSC V3.0
DSC Oat•• : 18-Deo-~7 T lm.. 121 321 49 Fil•· DATA.17 ee1 Operators AMENSON Plolted1 18-Deo-87 14127119
1.s~--------t-~-+-~t--+~-t-~+-__, __ .....,..~-+-~~--t~-+~-+-~t--+~-t-~+----1~---~--~t--T
1. 2
"· e
" ~ S.4 .... • ·o -LL S. S
;-g l
-s. 4
-e. e
-1. 2
-ae
------ .. 1 i··----
-se -40 -30 -2" -lS 0 12 20 ' DuPont 1090 Temperature (°C)
Figure 6(a). DSC thermogram of B2975 at 2 deg/min scanning rate.
,.,, • E " • 0 .....
LL
~ u • :c
Somplet ASPHALT 82975 Stz., 13. 4 MG Ra+.e1 5 DEG/MIN DSC
Dae•• 2-Apr-87 Time• 8135144 F1le1 ENUSTUN.19 EXT.07 Operalor1 AMENSON
ProgretN I n+.erao+. i ve DSC V3. 0 e -'-~t---+--+---1~....,~t---+~+-~~-+---1---+---+--+~-+---+
· Plol+.ech 2-Apr-87 .131 48a 19
-1
-2
-3 +5.5".
-4
-s
-8
-7
-SI -411 -· -28 -11 • 18 81 411 51 T Clll'lp•ra+.ure (°C) OuPon\ 1090
Figure 6(b). DSC thermogram of B2975 at 5 deg/min scanning rate.
...... \0
"" .. e "" • 0 -LL. ~ u :!
Samples ASPHALT 92975 Stzea 14.9 MG Ro~ea 11 DEG/MIN DSC
Da\e1 2-Apr-87 Time• 8116136 F&l .. ENUSTUN. 18 EXT. 07
Progr-a• In\•rao\lv• DSC V3. B Op•,..~OM AMENSON Plo~~eda 8-Apr-87 81 281 59
-18+--t---+---i---+--+-~~-+----t---+--+---t---+-~ ............ ~+--+~-+-~I---+-~+--+~+--+
-29
-22
-zs.s·
-24
-213 .15•
-28
--. ----38
-32
-sa -- -311 -28 -11 8 18 Temp.,..a~ur• C°C>
..a 5" DuPon~ 1''90
Figure 6(c). DSC therrnograrn of B2975 at 10 deg/min scanning rate.
N 0
21
discussed later. Also, there exists another inflexion point in the present
thermograms at a much lower temperature which corresponds to what these authors
consider as the glass transition point.
It appears that there is no correspondence between calorimetrically and
volumetrically determined transition points. It is possible that the transition
0
reported by Schmidt et al. (1966) as glass t,ransition in the vicinity of +5 C is
a volumetric manifestation of the above mentioned endothermic transformation.
Our previous experience is also such that glass transition points of an asphalt
sample determined by DSC do not correlate with thermomechanical results (*).
This state of affairs casts a shadow of doubt on the significance of the
glass transition points of asphalts, whether determined by calorimetric or by
volumetric measurements. Similar views were also expressed by Sisko et al.
(1968) and Jongepier et al. (1969) to the effect that the glass transition point
is an unsuitable parameter to describe the temperature dependence of rheological
properties of asphalts. In spite of this criticism, we consider that DSC of
asphalts may prove to be useful in indicating transformations of other kinds
related to their low-temperature susceptibility, as will be discussed later.
2.2.4. X-ray diffraction: X-ray diffraction spectra of asphalts have been used
for their structural characterization in relation to their quality (Williford,
1943; and Lee and Demirel, 1987).
All 12 original asphalt samples and their TFOT residues were subjected to
X-ray diffraction analysis by 8 - 28 scanning, using monochromatized CuKa. beam
with 1.54 A wavelength. The samples were molded in circular Plexiglas holders
exactly flush with their brim. The cross section of a sample holder is seen in
Fig. 7.
(*) Private communication with E. I. DePont de Nemours & Company, Wilmington, Delaware, 1971.
22 .
. c: I ~ --~3fl~~ ' I
Figure 7. Cross section of x-ray analysis sample holder.
3. RESULTS
3.1. Rheological Properties
Penetrations at 5 and 25°C (41 and 77°F), viscosities at 60 and 135°C and
softening points of the 12 original asphalt (O) samples as well as their thin
film oven test residues (R) are given in Table 1. While all 12 samples
generally met AASHTTO M226-2 specifications, variations between samples and
between suppliers within given viscosity grades existed. The variability in
penetrations are shown in Fig. 8; the variability in viscosities are shown in
Figs. 9 and 10. By far the most uniform results were observed in softening
points (Fig. 11).
23
Table 1. Rheological properties.
Sample I ·Sp.Gr. P25 P5 VIS 60 VIS 135 S.P ID I @ 25/25 poise c.s C
.. _ .. ____________ I __ . ______________________________________________ _ I
Jos-01-0 I 1.024 162 16 654.0 232.8 41.5 JOS-01-R I 1. 027 98 15 1369. 6 309. 3 48. 0
I J05-02-o I 1.019 160 1s 493.3 213.0 41.5 J05-02-R I 1.032 79 11 1528.1 336.7 50.0
' Kos-oi-o 1 1.023 193 22 556.o 225.o 40.5 KOS-01-R I 1.026 103 13 1272.7 334.7 49.0
I KOS-02-0 I 1.023 182 17 483.7 211.8 40.0 K05-02-R I 1.026 95 13 1159.5 321.5 48.0
-----------'--------------------------------------------------!
J10-01-o ! 1.031 91 11 1466.6 329.5 48.o Jl0-01-R I 1.034 60 8 2640.4 453.9 54.0
I J10-02-o I 1.019 92 11 1091.2 312.1 45.s Jl0-02-R I 1.031 59 10 2639.9 469.5 53.0
I Kl0-01-0 I 1.028 123 15 1024.3 307.1 45.5 Kl0-01-R I 1.030 72 9 2540.7 457.4 51.5
I Kl0-02-0 I 1.028 102 11 1078.9 311.2 46.0 • Kl0-02-R I 1.031 61 10 2734.9 461.9 53.5
---------·------·-- I ------------------------------------------------------!
J20-01-o I 1. 020 78 12 2444. 6 448. 1 so. o J20-01-R I 1. 029 57 10 5062. 5 660. 7 56. 0
I J20-02-o I 1.010 66 8 1020.0 450.8 49.5 J20-02-R I 1. 029 50 8 3929. 3 592. 8 54. 0
I K20-0l-O I 1.031 75 10 1893.3 430.3 49.0 K20-01-R I 1.034 49 8 4647.6 618.2 55.5
I K20-02-0 I 1.031 67 7 2010.0 428.3 so.o K20-02-R I 1.034 43 6 5000.9 581.4 55.5
P25 : penetration @ 25 C, 100 g, 5 sec. PS : penetration @ 5 C, 100 g, 5 sec. VIS 60 · : viscosity @ 60 C. VIS 135 : viscosity @ 135 c. S.P : R & B softening point. O original. R : thin film oven test residue.
E E 0
' ...
E E 0 ... ' ...
24
PENETRATION AT 41 F 22
20
18
16
14
12
10
e
6
4
2
0 J1-0 J2-0 K1-0 K2-0 J1-R J2-R K1-R K2-R
PENETRATION AT 77 F 200--~~-'-~~~~~~~~~~~~~~~--~~~~~~~~~~
190
180 170 160 150 140
130 120 110
100
90
80 :70 60
50 40
30 20 10 o_._....,.~~~"""'~o....-J"-..M~.c.;M.._.~~~,....~~""-.J,....;i""""'u;,},,'--~""""'.QI.--"~"""'~
J1-0 J2-0 K1-0
ISSI AC-5
K2-0 J1-R
~ IDENTif1CATION ~ AC-10
J2-R K1-R K2-R
IZZI AC-20
-·
Figure 8. Penetration at 25°C (77°F) and at 5°C (4.J, °F).
'f :J I .
11 :J J
t~I I
It ll
I
• II
4
:s
2
VISCOSllY AT 60 C, AC-5
"' "'
VISCOSllY AT 60 C, AC-10
,,, .12 K1 ICI
~~"
VISCOSllY AT 60 C, AC-20
Figure 9. Viscosity at 60°C (140°F).
25
26
lllllCOlllY Af ,. c, AC-I 7DO
eao
llOO
• 400
I 300
200
100
0 JI .II IC1 IC2
~~It
VISCOSllY AT 1llll C, ~10 7DO
eoo
500
i 400
I JOO
200
100
0 J1 .. .. IC2
~~It
• I
Figure 10. Viscosity at 135°C (275°F).
27
RING AND BALL SOFTENING POINT, AC-5 . --·------------------.
u
l I
RING AND BALL SOFTENING POINT, AC-10
u
1 I
RING AND BALL SOFTENING POINT, AC-20
u
l I
Figure 11. Ring and ball softening point.
28
Asphalt cements of high temperature-susceptibility may contribute to
rutting at high pavement temperatures and cracking at low pavement temperatures.
Temperature susceptibility of an asphalt can be evaluated by using the Shell
Bitumen Test Data Chart (BTDC), the Penetr.ation Index (PI), the Pen-Vis Number
0 0
(PVN) based on viscosity at 60 C or viscosity at 135 C, the
viscosity-temperature susceptibility (VTS), and the Asphalt Class Nuinber (CN).
The basic rheological data as plotted on BTDC are shown in Figs. 12 and 13; and
the derived PI, PVN, VTS and CN of the asphalt cement samples studied are given
in Table 2.
The CN shows the difference between measured and predicted penetration at
25°C. A small negative or positive CN value indicates a Class S (straight run
with a straight line, temperature-viscosity~penetration plot) asphalt. High
positive CN values indicate Class W (waxy) asphalts, and high negative CN values
indicate Class B (blown) asphalts. Either case reflects substantially high and
low· temperature-susceptibility. ·While a few of the samples showed somewhat
higher (e.g. J2 samples) or lower (e.g. Kl samples) temperature susceptibility,
the results on temperature susceptibility, especially measured by VTS and PVN,
were remarkably uniform. These are shown in Figs. 14-17.
Low-temperature asphalt stiffness has been correlated with pavement
cracking associated with nonload conditions. The low-temperature behavior of
asphalts can be evaluated either by estimating the temperature at which asphalt
reaches a certain critical or limiting stiffness or by comparing the stiffness
of asphalts at low temperatures (long loading times).
Table 3 presents the results of estimated low-temperature cracking
properties of the 12 asphalts. The properties include cracking temperature
(CT), temperature corresponding to asphalt thermal cracking stress of 72.5 psi
( 5 0 0 5 x 10 Pa), based on penetrations at 5 C and 25 C, temperature of equivalent
29
Table 2. Temperature susceptibility.
I Sample I CN Pim VTS PVN,60 PVN,135
ID I · ---------------- I -----------------------------------·-------------
! J05-01-0 I 5.17 -0.327 3.538 -0.432 -0.510 J05-01-R I 2.44 0.060 3.601 -0.462 -0.639
I J05-02-0 I 11.00 -0.378 3.497 -0.784 -0.675 J05-02-R 1 6.38 -o.b~6 3.569 -0.689 -o.742
! K05-01-0 I 5.09 0.028 3.497 -0.306 -0.344 K05-01-R I 4.76 0.510 3.503 -0.459 -0.462
I K05-02-0 I 8.73 -0.455 3.490 -0.580 -0.526 K05-02-R I 8.30 -0.038 3.498 -0.691 -0.614
-------------- I -----·--------"-----------------------------------! . J10-01-o I 3.67 -0.111 3.571 -0.509 -0.624. Jl0-01-R I 4.67 0.206 3.540 -0.552 -0.595
I J10-02-o I 9.98 -0.884 3.504 -0.001 -0.694 J10-02~R I 5.75 -0.072 3.515 -0.577 -0.565
I Klo-01-0 I 4.82 0.056 3.483 -0.400 -0.390 Kl0-01-R I 1.28 0.091 3.522 -0.309 -0.393
I Kl0-02-0 I 7.94 -0.414 3.494 ~0.654 -0.586 Kl0-02-R I 3.60 0.132 3.542 -0.492 -0.554
~----·---------- I -----------------------------------------------!
J20-01-o I -0.01 -0.012 3.524 -0.221 -0.333 J20-01-R I -3.67 0.526 3.499 0.016 -0.125
I J20-02-o I 11~15 -0.658 3.411 -0.110 -0.507 J20-02-R I 4.10 -0.247 3.487 -0.433 -0.411
I K20-01-0 I 6.84 -0.451 3.453 -0.548 -0.438 K20-01-R I 1.08 0.039 3.514 -0.300 -0.375
I K20-02-0 I 7.98 -0.488 3.481 -0.660 -0.564 K20-02-R ! 1.24 -0.264 3.589 -0.422 -0.586
CN : class number. Pim : measured penetration index. VTS : Viscosity-temperature susceptibility.· PVN,60 : Penetration-viscosity number @ 60 c. PVN,135 : Penetration-viscosity number@ 135 c. O original. R : thin film oven test residue.
tml\UOl.01""" tr-r-ir-r-.-r-r-r-"T"-rT r-,--,--~,-..-..-.--.--..-.-,
,, - - - r- - - r, '·-t-r- - - r--r-~ . ~-
•-r·
r- -r- . r-r- - r r-· - -,-r--r-,---r-,. +-+-!·-++ 1-1--i-t-+-+--+-
UIMTm.Olnm 1r-r-ir-r-,.-r-r-r"T"-rT-r-r-ri-r-r-r""T"""T"""T""l"""l ,, - - - r- - - - t-- - ,,
•1-+-iH--t-+-+-+-t--t--t- -
•Ill ·«I ·II ·211· ·8
- 1-t- 1--...-..-.-.-.... ·::-..
Figure 12.
~ l'.l_l I i~ AC-10
30
•!lllllll. l'IJSJS ·r-r-.--r....-·r-r-r· u/
. t-t-- -
~ Penetration
• Viscosity
e - R & B softening· point
'
- --- 1
-- .. - I
·-·>-- • ... -->-I
~~.ioJ ·_ ~ s::· : . - - I
BTDC of original (0) Jebro asphalts.
31 QfaQI, Olrrm 1,-,.-,,-,_,.-,..""T"-r-r--,-T-..-,-,--r--,--,--,-.,-,.-..-.--. ,, . - ,, 1--~-- - - ----~-·- -
--~· -:. ·.~~- ti1t8~--!-!~~~~~~~1i!~~'~!~!!itr££~~~~~~j~.--tt::~t2t=-3· ~--} .. +±_;,,,=_±_~±:_=±±:r_0"t_clr - - .. ·-··r-· :.~~.-:..~..=.- ·i-- ~- -- -+-+--+--+-+-+ - ::: - ....... ~ .J .. -~ .: ::',:... ~:::: . ~- - . ==~- . ~-::.' . - r·- - '"°- --f-- -1-- - 1-- ......... ,__ - ->--+-+-+-,__,_, -+--..-+"'...,.-+-""°'~,-+-+--+-+-+-+-+-+-1-i
· - ·-++-+-1-•H-+ +-+-+-1--1'-l-t·-t·--t'~~+-<t-,·'"",-t- +-t--,f--IH-t-+-+--+-+-+- ~- ,.._,.... ~ - -·· - . ".. . +-·+->-<,-.-+-<>-<>·
.. _,_ .... t--.~--·-·-
··r- - - --~-- ·+-+-HH'-1-t-+-+- -~ ·- ·+-+-+-+-+-+-+-1--1
,.._,__ __ . -- ~- - ·-'- .
r-- ---~--•-<--+-+-..__,__.__.. Hl-+-+-+-t-+-+-· ·--- r-r- · ~H ": ;'>,_._,...__._..._._-1-·+-+-+-·t--t H~-;-t--+-+-+-t--+-+-+-+-H-1-+-+-++-+-+-+ +-+-+-+·-i"<*-~" ,Ac,-to I -1--+··+-+-~I>..... .. ·-
t-+-·+-1--t--HH-t-t-t-- -- -- 1 AC-10
AC-5 • ".-'"~~:-"""~~_._...__.__.._...__._._.._.~_,_,_..-L--'--f-'-_._'-'--'-.._,_,__._,_,_\~\~..__.11_..._..l_._..._..__.__._._._..__,_L..L_,_.._,_,__,_L-J.~I ·•·•·•··•·• 20••»• 11t0•noaollD•llll•ia•111111111lllD!JDlll1lO
1llff1Allll. •c
Qtat.ra,Olrrm 1.-.-.....,. ...... -,...,.,...,.....,--,--,-,.-<"""',....,....,.....,.....,. ...... ..,....,.....,......,
" -I
r--·1-- ··1--t - '-'""· - .
::. --= -
- " +-+-+-HI-+-+· -
.. -·--r-· . ·-·t--,
---l-- I
1-Hr~-t-+-+·-+++-+--~·I-- -- -+-+-+-+-+-HH-+-+-+-+++-+-+-+-+-'~!\..-+....-·~·+-+-+-+-+-"l~HH-t-t·-l-·l-+-+-+-+-1--IHH-t-t- I .. ·i'-1-W AC-20
Hl-t-+-+-+-+-+-c--t-+-+-t-+-H'-l-+-+-+-+-+-1--1-+-+-+-+-+-+-·+--11-+-+-+-t-~'r+,-'k--+41'-ll-+-l._,~~-+-lC-+~-t-+-l--1-t-+---r-
' AC-10 AC-S
~~~~~~~~.._..__.._,_..__._.,_...__.__._.....__._..._,,_.._f-' ....... '-'-<-<-'--'--'-...t......L....L....__,_.._.._.._.__...._.__. .............................................. _._.._.._..._.._.._~, ·:ID ·411 ·II ·ID ·9 20 II 4D IO II D II ., Ill Ill II) Ill !JD Ill 1lO
T!-llll.'t
Figure 13. BTDC of original (0) Koch asphalts.
PENETRATION INDEX, AC-5
IC .•
PENETRATION INDEX, AC-10
0.1
-0.1
-o.a
I: -u -oA
'
-0.S
-0.1
-0.7
-o.a
-0.t-'-~-.-~~-=====T-~~~~--,.--~~~~-.---'
.11 IC1
PENETRATION INDEX, AC-20 a.a~~~~~~~~~~~~~~~~~~~--.
0.5
0.4
0,3
G.2
0.1
-o.a
-G.l
-oA
-0.S
-0.1
-0.1--~..---~~~-.-~~~~~,~~~~~-.-__,
.It Kt ICl
Figure 14. Penetration index.
32
33 PVN AT 60 C, AC-5
PVN AT 60 C, AC-10
PVN AT 60 C, AC-20
Figure 15. PVN at 60°C (140°F).
PVN AT 135 C, AC-5 34
PVN AT 135 C, AC-10
-u~'~,,r--~~~----,,---~~~--.~~~~--.~__J J1 IC1 ICZ
PVN AT 135 C, AC-20
Figure 16. PVN at 135°C (275°F).
vrs. AC-5 35
• lLI
ll
I.I
e 2
l.S
o.a
0 JI J2 Kl ICZ
~~II
vrs. Ac-10 •
lLI
ll
I.I
~ 2
I.I
o.a
0 JI J2 ., ICI
~~II
vrs. Ac-20 •
lLI
ll
I.I
~ 2
t.I
Figure 17. Viscosity temperature susceptibility.
36
Table 3. Low-temperature cracking properties.
~--'-·---··- ·------'':'-.~T_··- --·----·-- ---.-:-;-----------------:,,....-.-··· ~.=--·--·--- -·-·- -·-- --··. ·····- ·--· ··--·· ··-·- ·-··----···-··· .. ·-· ---· ··-··· -···- ·-·
Sample I CT TES S,-23 S,-29 _. :~;- . _:ID ! .. ''h'c c ~si , .. . .. ksi
·--------·--_ --~----··---- I --·------""------=---------------------------·--·--------·-----c-----··--· I , • ',
J05-01..:o J05-01-R
J05-02-0 J05-02-R
I K05-0l-O I _K05-01-R !
I
-40.5 -45.0
-40.0 -40.0
-45.0 -42. 0.
-46.5 -47.0
-46.5 -40.0
-49.5 -43.0
0.406 1. 305
0.348 1.740
0.210· 1.015
1.160 2.610
1.595 4.350
0.725 1.740
ko5-02-o 1 -4o.o -45.o 0.290 0.125 K05-02-R ! -43.0 -42;0 · 1.015 3.625
·---'--------- I --------------~-----------------~-'-----------! -Jl0-01-0 ! -38.0 -40.5 1.450 J.10-01-R I -37. 5 -37. 0 2. 900
I J10-02-o I Jl0-02-R !
I Kl0-01-0 ! Kl0-01-R !
!
-38.5 -42.0
-42.5 -37.5
.:1
-34.5 -36.0
-44.5 -38.5
2.755 3.335
0.580 1.740
2.900 4.350
5.800 7.250
1.450 5.800
K10~02-0 ! -38.0 -42.0 1.305 3.045 K10-02~R ! -41.5 -36.5 2.030 5.800
-----------'-------------------------------------------. I J20-01-o I J20-01-R !
l J20-02-0 ! . J20-02-R I
! K20-01-0 I K20-0l-R !
I K20-02-0 I K20-02-R I
-42.5 -39.0 -42.5 -36.0
-36.5 -32.5 -39.0 -34.5
-39.5 -36.0 -39.0 -34.5
-34.0 -35.0 -35.0 -32.5
crack1ng temperature.
1.740 2.175
3.625 4.350
2.900 4.350
2.900 7.250
3.480 4.350
10.150 8.700
7.250 8.700
7.250 14.500
CT TES temperature of equivalent stiffness at 20 ksi,
10,000 sec. s,-23 s,-29 0 R
stiffness at -23 C, 10,000 sec. stiffness at -29 c, 20,000 sec. original sample. thin film oven test residue.
37
asphalt stiffness of 20,000 psi at 10,000 sec loading time (TES), estimated
stiffness at -23°C and 10,000 sec loading time, and stiffness at -29°C and
20,000 sec loading time. The following can be observed:
• Softer grade AC-5 had a lower cracking temperature and reached a
critical stiffness of 20,000 psi at a lower temperature than
harder asphalt AC-20.
e Within a given viscosity grade, cracking temperatures of asphalts
could vary by as much as 5°C.
• Low temperature stiffness values for asphalts of a given
viscosity grade could differ by a factor of 4.
The effect of heat, as determined by viscosity at 60°C (14cJF) and
0 0 penetration at 25 C (77 F), on the thin film oven test residues, are given in
Table 4 and shown in Fig. 18. Viscosity ratios were uniform at between 1.8 to
3.1 (all meeting AASHTO M226, Table 2, maximum ratio of 5); penetration ratios
varied between 0.49 and o.76.
The resistance of asphalts to hardening during hot-mixing and their
temperature susceptibilities are indirectly specified in AASHTO M226, Table 2.
These important properties are plotted in Fig. 19 in terms of PVN and viscosity
ratio at 60°C (140°F). Except for the second set of samples from Jebro,
asphalts supplied in Iowa appeared to be rather uniform. Relationships between
viscosity at 60°C (140°F), penetration at 25°C (77°F) and PVN of the 12 asphalts
are presented in Fig. 20 with reference to AASHTO M226.
The properties of recovered asphalt samples from Research Project HR-217,
80 months after construction, are given in Table 5. While aging has increased
the viscosities, the average PVN of -0.64 for Wood River asphalts and -0.97 for
Sugar Creek asphalts, changed little from those reported by Marks and Huisman
38
Table 4. Thin film oven test hardening.
I sample I Viscosity ratio Penetration ratio
ID I @ 60 c @ 25 c ____________ I __ ~-----------------------------------------------
1 J05-01 I 2. 09 o. 60
02 I 3.10 o.49 I
Jlo-01 I 1. 00 o. 66 02 I 2.42 o.64
I J20-01 I 2.01 o.73
02 I 2.15 o.76 ___ . _________ I ______ .1__. _________________________________________ _
I K05-01 I 2.29 o.53
02 I . 2.40 o.52 I
Kl0-01 I 2.48 0.59 o2 I 2.53 o.60
I K20-01 I 2.45 0.65
02 I 2.49 o.64
O·
I
I
39
Retained penetration @ 25 C
J1 J2 K1
lSSJ AC-05 m ldentlflcotlon
AC-10 ~ AC-20
Viscosity ratio @ 60 C 3.2""T'""~~~~~~~~~~~~--~--~~~~~---
3
2.8
2.1
2.4
2.2
2
1.1
1.1
1.4
1.2
o.a 0.1
0.-4
0.2
K2
o ...... ~~"""".....,..._~--~-..,~.._:u.. __ .-..~"'"'~1.A.ocw..~~..._~~1.A.AJ J1 J2
Sm!!1'J!I ldontlflcatlon ~ AC-10
1<1 K2
Figure 18. Retained penetration and viscosity ratio, thin film oven test.
0
-0.1 -
-0.2 -
-0.3 -
u.. -0.4 -0
"'" ... ~
-0.5 -
z 6: -0.6 -
-0.7 -
-0.6 -
-0.9 -
-1
0
0
-0.1 -
-0.2 -
-0.3 -
u.. -0.4 -Ill I' N
~ -0.5 -
z 6: -0.6 -
-0.7 -
-0.B -
-0.9 -
-1
0
PVN, 140 VS VISCOSITY RATIO
+ J20-1
+ KOS-1
+ + K10-1
JOS-1 +
J10-1 + K:i0-1
KOS-2 .p-
~t:P--22
+ + J20-2 + JOS-2
J10-2
I I I
2
VISCOSITY RATIO {R/O) AT 140 F
PVN,275 VS VISCOSITY RATIO
I
+ + J20ds-1+
K1.p-1 K20-1
+I- + J~5-+2
+ J10-1
I
2
~ffi=--~ +
J10-2
+ JOS-2
I
VISCOSllY RATIO (R/O) AT 140 F
I
4
I
4
Figure 19. PVN vs viscosity ratio.
40
..
(/) w (/)
0 a.. z -LL. 0 0 v -~ >-1--~ u CJ) ->
41
rooooo,.._ __ ~~l"'""-"~-r.-r-rn~~~~~~l'."T~-~-L·~ .. ~·~··=·i:::::::··::::I::::!::r:::W:w::t• r I »· '•••· '~» ... , .... ,,,., ......... ,o)~··•l .. •·l·"·i .. ·· ··1·····•'1• '·I
'\. • . • . . . :~~· ••. ;,. . ;,, ··-·, ·!-·~:(~ ..• , ... . 1.~~ ••• .... - ~I~~ -·· • •· ··I··•·• .. · · · ·t ··· ... :}"" · ·
Figure 20. Relationships Between Viscosity at 140°F in Poises, Penetration At 77°F, and Temperature Susceptibility;.
Table 5 .
. sample
WOOD RIVER
Surface Binder Base
SUGAR CREEK
Surf ace Binder Base
42
Properties of recovered asphalts
P25
43 71 56
24 35 26
VIS60 poise
4806.0 1701. 3 2471.2
8268.3 3624.3 4817.1
PVN60
-0.460 -0.742 -0.720
-0.763 -1.010 -1.137
P25 : penetration @ 25 C, 100 g, 5 sec. VIS60 viscosity @ 60 c. PVN60 : Penetration-viscosity number @ 60 C.
•
•
43
(1985). The significance of these data will be analyzed during Tasks 3 to 6 of
the study in relation to chemical changes and performance data.
The results of viscoelastic measurements at +5°C described in 2.2.1 are
given in Figs. 21 and 22, plotting viscosity and elasticity indices against
time. It will be clear from the description of these measurements that the
viscosity data presented pertain to Newtonian viscosity, i.e. viscosity at zero
shear rate.
Reviewing the viscoelastic data, one can observe that the rheological
properties of these samples exhibit strikingly different dependence on their
thermal history and time. Some properties do not stabilize even after seven
days. The estimated viscoelastic properties of these samples and their trends
are summarized in Table 6.
3.2. Gel Permeation Liquid Chromatrography (GPLC)
The results of GPLC runs with 12 virgin asphalt samples, their TFOT
residues and six recovered core samples as described in 2.2.2 are given in the
form of chromatograms in Appendix I. The estimated large molecular size .(LMS)
ratings of these samples as defined by the Montana State University research
group (Jennings. et al., 1980; 1982; and 1985) are tabulated in Table 7. In the
third column of this table tabulated are the fractional change of LMS upon TFOT,
except the last two values. The latter are the fractional change of LMS, going
from the base course to the surface course sample of the Sugar Creek and Wood
River projects, respectively.
3.3 Thermal Analysis
The results of DSC tests described in 2.2.3 are presented in Appendix II as
thermograms. The low temperature inflexion points on these thermograms, as
interpreted by Noel et al. (1970) and Albert et al. (1984) as glass transition
points, tg, are tabulated in Table 8. The rest of the thermograms, which have
44
r::::- ·1---.-::.. _ -~ - .-- ·+ _,,_.=
6
5
4
£
t
•
•
0.1--'--'---''---'~-'--'-~-'---'---'~-'--'--'--'-'-----'~-'--'--'--'-'-'~~-'-~~~
0 Hi-.s.
Figure 21. Viscoelastic properties of JOS-01-0, Jl0-01-0 and J20-01-0 at +5°C.
•
e
l
•
8.
6
5_
4
7
4 - -
3.
2
,9-• S ..
,] _
,3
,2
o.: ·-·--0
r- r·
····!·
. . . . . . .· . ~-- .:.....:..:....:..--.-~·~ --· .. -· .. : ....... , . .
. ----· ----------· -·---·
Figure 22.
45
·1--·
-- 1 :_i .. ;.
192
Tl~E Hrs.
Viscoelastic properties of SC-SU and WR-SU at +5°C.
46
Table 6. Viscoelastic properties of thermal cycled samples at +5 C. n : Viscosity, MP G : Elastic shear modulus, psi
I I I % variation I
3rd day valu~I in the first 3 days after I after cocilingl ____________________________ _ from +25 C I I
Sample cooling I warming I from +25 c I from -30 c l ·-----·-----··---------· _______ :.._: ______ I _____________ _ I I . I n G n G I n G
__ ... _ .. __ . ______ I --------·----------- _______________ I _____________ _ I I . I I
J05-01-0 I 225 12 31 0 I 29 -38 Jlo-01-0 I 1580 16 44 -18 I J20-01-o I 6990 13 93 -38 I
----------:-------------- ---------7---~:--------------sc-s I 29200 130 11 o I 160 650 WR-S I 9720 54 43 20 I 16 -14
* % change
n G
6 67
-72 -94 43 16
* % fractional change in initial value observed after warming from -30 C ~elative to that after cooling from +25 C.
Table 7.
J05-02-0 J05-02-R
K05-0l-O K05-01-R
. K05-02-0 K05-02-R
SC-Ba SC-Bi sc..:.s
WR-Ba WR-Bi WR-S
47
Results of HP-GPC analyses.
20.6 24.0
30.2 31.4
27.2 30.7
21. 8 24.9
24.9 27.4
30.8 32.8
+16
+4
+13
+14
+10
+7
2.26 2.42
2.12 3.25
0.64 1.06
0.64 1.02
2.26 2.78
1.46 2.02
0.36 0.74
1. 85 2.92
0.88 1. 50 1. 78
1. 68 3.34 1. 89
+71
+53
+66
+59
+23
+38
+105
+58
+102
+13
48
the same general appearance as reported by the latter-authors, consist of two
shallow endothermic peaks. The peak temperatures ti, tz and their mean tin are
also tabulated in Table 8. These regions were analyzed in the manner described
by Albert et al. to determine.the enthalpies of transformation fiH given in the
last column of this table.
3.4. X-ray Analyses
The X-ray diffraction spectra obtained by 8 - 28 scanning of the original
samples and the TFOT residues, as described in 2.2.4, as well as of an empty
sample holder to represent the background, are presented in Appendix III.
According to Williford (1943) the height of the shoulder of the spectral
curve at low angles is a measure of the quality of the asphalt. This height
above the background (at 28 = 4.83 degrees) for various samples and their TFOT
residues are tabulated in Table 9.
Also indicated are the qualitative changes in the shoulder height and the
peak height upon TFOT for each sample.
3.5 Correlations
Poor field performance of asphalts under extreme climate conditions are
attributed mainly to low-temperature susceptibility of their rheological
properties (Schmidt, 1966; Breen et al., 1967; and Albert et al., 1985).
It has long been attempted to correlate some low temperature transitions in
asphalts, which are believed to effect their low-temperature rheology, such as
glass transition (Schmidt, 1966; Breen et al., 1967) and phase transformations
(Noel et al., 1970; and Albert et al., 1985) to their field performance.
One of the most fundamental, direct and conclusive approaches to correlate
rheological properties with another physicochemical property was made in the
Central Laboratory of Highways and Bridges in France .(Brule et al., 1987). The
researchers of this organization, starting from the experimental fact that
49
Table 8. DSC test results.
! Sample I t t 1 t 2 tm Enthalpy change
! g J/g ----------- I -----------·----------------------------------------------
! J05-01-0 ! J05-01-R I
I J05-02-o I J05-02-R I
! K05-01-0 ! K05-01-R I
!
-31 -29
-29 -30
-26 -26
17.0 16.0
17.0 17.0
17.5 17.0
47.5 48.0
41.0 39.5
53.0 47.0
32.0 32.0
29.0 28.0
35.0 32.0
12.0 10.1
10.3 15.0
8.2 a.a
K05-02-0 I -30 16.0 47.0 31.5 a.a K05-02-R I -29 17.0 53.0 35.0 8.4
--------~-'-------------------------~----------------------------!
Jlo-01-0 I Jl0-01-R !
I J10-02-o I Jl0-02-R I
l Kl0-01-0 I Kl0-01-R I
I
-30 -31
-32 -30
-31 -30
16.5 16.0
16.5 16.5
17.0 17.5
47.5 45.0
48.0 48.5
41.0 48.0
32.0 30.5
32.0 32.5
29.0 33.0
11. 2 13.9
9.3 10.5
6.9 7.5
Kl0-02-0 I -29 17.0 48.0 32.5 6.8 Kl0-02-R I -30 17.0 46.0 31.5 6.7
·---------·-·- --- I ---···-----------·-----·---------------------------------------!
J20-01-o I J20-01-R !
I J20-02-o I J20-02-R I
I K20-01-0 I K20-01-R I
I
-35 -35
-30 -29
-25 -22
16.0 17.0
16.5 16.0
17.5 19.5
44.5 47.5
47.5 53.0
47.5 47.5
30.0 32.0
32.0 34.5
32.5 33.5
11. 4 9.7
9.7 10.6
5.7 4.8
K20-02-0 I -26 22.0 50.5 36.0 6.0 K20-02-R I -30 29.5 53.0 41.0 7.8
-----·--·------- I -------------------------------------------------------------
SC-Ba SC-Bi sc-s
WR-Ba WR-Bi WR-S
! . ! -26 17.0 50.5 34.0 9.6 ! -31 16.o 44.o 30.-0 11.2 l -30 16.5 48.0 32.0 10.6 I I I !
-37 -35 -35
15.0 14.0 16.0
44.5 44.0 43.5
30.0 29.0 30.0
10.8 13.3 10.7
Table 9.
!
50
Shoulder height of x~ray diffraction spectrum at two theta = 4.83 degree.
Sample I Shoulder height change in change in I counts x 10 shoulder height peak height
---------------- '--------·---·--------------------------------------------~-·--·-------!
J05-01-o I 33 J05-01-R I 37 + 0
I J05-02-o I 26 J05-02-R I 40 + +
K05-01-0 K05-01-R
K05-02-0 K05-02-R
I . 26 37
36 36
Jl0-01-0 43 Jl0-01-R 37
Jlo-02-0 I 44
+
0 0
Jl0-02-R I 32 + I
Kl0-01-0 ! 34 Kl0-01-R ! 26 +
! Kl0-02-0 I 25 Kl0-02-R I 25 0 +
---------- ' ------------------~--------------------------------------!
J20-01-o I 25 J20-01-R I 41 +
I J20-02-o I 48 J20-02-R I 13
I K20-0l-O ! 36 K20-01-R I 18 +
! K20-02-0 I 25 K20-02-R I 39 +
51
non-Newtonian behavior of asphalts is enhanced at lower temperatures, and
considering the associative interactions between asphaltene micelles leading to
sizeable colloidal agglomerates, were able to correlate the GPLC profiles and
the asphaltene contents to rheological properties.
For this correlation they made use of the intensity of a sharp GPLC peak at
a molecular weight of greater than 100,000 obtained by a fast elution (3.5
0
ml/min.) using two 30 cm long Styragel columns of 1000 and 10,000 A pore sizes.
The purpose of this fast method was preventing the breaking up of asphaltene
agglomerates in the presence of the THF solvent. They also showed that TFOT
increases this agglomeration significantly.
+ The message in the results of the French research group is that the gel +
sol equilibrium in asphalts has an important bearing on their rheological
properties. Since agglomeration (gel formation) is exothermic, at low
temperatures the gel form, at higher temperatures the sol form is predominant at
equilibrium. The DTA studies of this group, as well as the DSC studies of Noel
et al. (1970) and Albert et al. (1985) in the absence of oxygen clearly shows
endothermic transformations as temperature is raised in the range of -S°C
through +80°C.
Although this transformation is referred to as melting of the crystallized
asphaltic components by Noel et al., as dissolution of these components in the
matrix by Albert et al., and vaguely as melting by Brule et al.; it may solely
or partly be gel to sol transformation following a sol to gel transformation
taken place at lower temperatures.
It appears, therefore, that the following factors may effect the asphalt
rheology at low temperatures:
(a) Predominance of agglomerates of asphaltene micelles,
(b) Presence of crystallizable components.
52
The LMS fraction defined and estimated by the Montana research group using
a GPLC method as described in 2.2.2 includes the agglomerated asphaltene
molecules in addition to other asphaltic components. If the concentration of
these agglomerates happens, for some reason, to be proportional to or be a
monotonic function of the LMS content in general, and further if they are
responsible for low temperature susceptibility of the asphalt (factor a), then
the LMS rating of a sample is expected to measure its poor low-temperature
performance. This is exactly what has been put forward by the Montana research
group on grounds of their experimental findings.
Whatever the nature of the endothermic transformation observed in thermal
analysis (factors a and/or b) is, it follows from the DTA results and the ideas ' . ,, . .
put forward by Brule et al. (1987) and the DSC results of Noel et al. (1970) and
Albert et al. (1985) that the location of the endothermic transformations on the
temperature scale described above may also characterize the low-temperature
susceptibility of the asphalt. For instance, the larger the endothermicity of
this transformation and higher the temperature range in which it occurs, the
more susceptible may be the sample.
As associative interaction between asphaltene molecules promotes a
structural order in the system, such an interaction is also expected to reflect
on x-ray diffraction spectra of the sample.
The experimental data presented in Section 3.1 through 3.4 will be reviewed
below, in relation to these expectations. Since no engineering service
information is available at this stage of the present project, except in the
case of samples labelled as SC and WR, this review will be confined to parallel
comparisons of various proper~ies between samples, and between artificially aged
and unaged samples.
53
3.5.1 Rheological properties: An inspection of viscoelastic data presented in
Figs. 21 and 22, and in Table 6 reveals that:
(a) All samples studied exhibit an increase in viscosity at +5°C after
cooling from +25°C in various extents. This trend appears to be more pronounced
in more viscous asphalts.
(b) With the virgin asphalts of high viscosity this increase is
accompanied by a decrease in elastic modulus. Some parallelism is observed
between this drift and their LMS rating,, as well as the peak-height of their
X-ray diffraction spectra.
(c) Among the samples conditioned at -30°C, the effect of low temperature
on viscoelastic properties of SC-SU is dramatic and in the opposite direction of
those of the other two samples. A drastic fall followed by a fast rise,
especially in its elastic modulus, deserves attention. Before low temperature
conditioning, the viscosity and elastic modulus of this sample are also
incomparably greater than those of the others. Comparing the two core samples
(SC-SU and WR-SU) one observes that the low-temperature (-30 C) susceptibility
of SC-SU is far greater. It is significant that the effect of natural aging in
the pavement as reflected on their LMS ratings (Table 7, column 3) is also much
greater in the case of the Sugar Creek sample.
(d) From the viewpoint of its time dependence after a cold shock, the
elastic modulus appears to be more characteristic and discriminating than
viscosity.
3.5.2 GPLC: The results on %LMS defined by MSU method as given in Table 7
showed the following:
1. The %LMS of original asphalts studied ranged from 20.6 to 30.9, all
higher than the maximum allowable %LMS of 16-17% for the Montana climate
(Jennings and Pribanic, 1988).
54
2. The %LMS of asphalts in a given viscosity grade varied up to 7.4%
between samples from the same supplier; this difference was as high as 9.6%
between samples of different suppliers.
3. While %LMS iricreased with viscosity at 140 F for asphalts from Jebro,
this was not the case for Koch asphalts which had relatively higher %LMS but in a
narrow range between 27.2 to 30.8.
4. Thin film oven treatment increased %LMS by an average of 2.87% (1.2
to 3.8%) to a low of 24% for J0502 and a high of 33% for J2001._
The last observation means that the GPLC technique can be used as a
reliable test to monitor aging, as concluded also by Brule et al. (1987) who
used a different and accelerated modification of the Montana method as described
earlier.
A comparative analysis of the GPLC size distribution curves shows that the
fractional increase in the largest detectable molecular size region (earliest
elution) as a result of TFOT, is the largest among the other regions of the LMS
fraction as defined by the Montana research group. Although this version of the
GPLC method differs from that used by Brule et al. in that the former is unable
to detect all asphaltene agglomerates in the 100,000 molecular weight range due
to their peptization during testing as mentioned earlier, we believe that the
early-eluted fraction is made up by the remnants of undissociated agglomerates,
and that the observation just mentioned is the result of formation of extra
agglomerates induced by TFOT.
Then, the early-eluted fraction content of a sample is expected to be
approximately proportional to the original agglomerate concentration, and thus
is a more sensitive index than LMS to characterize aging, as well as the low
temperature susceptibility of the sample.
With this consideration, in Table 7 we also tabulate (LMS) 18.125, the
percentage of the fraction eluted within 18.125 minutes taken from the
55
printouts, and the fractional change of this fraction upon TFOT. It will be
noted that the fractional change of (LMS) 18.125 due to aging is much larger
than that of LMS defined by the Montana group.
In Fig. 23 (LMS) 18.125 is plotted against LMS for all the samples studied.
The trend shown in this plot is an evidence of approximately linear dependence
of the agglomerate concentration on the LMS rating, as hypothetically postulated
earlier in Section 3.5.
Repeated tests on a sample appear to yield (LMS) 18.125 values in close
agreement with each other. .However, to take care of day-to-day drifts in the
performance of the GPLC equipment, the adoption of a comparative procedure using
an external standard (such as the sample J05-0l-0) to determine the correct
cutoff time, is recommended for future work.
No correlation is observed between GPLC results and X-ray diffraction
results.
A quick search for correlations between the standard rheological indices
tabulated in Tables 1 through 5 and the LMS ratings shows that neither VTS nor
CT correlates with LMS, whereas there is a weak correlation between PVN and LMS
(r = -0.59) meaning that the samples of higher LMS content tend to behave less
temperature susceptible.
Glover et al. (1988) at Texas A&M University, using two columns and RI
detector, and defining LMS and SMS by retention times of 25 and 30 minutes (the
chromatograms were divided into three equal-time sections between 20 and 35
minutes), found relationships between viscosity temperature susceptibility (VTS)
and the molecular size distribution by HP-GPC: the lower the %LMS and the higher
the %SMS, the higher the temperature susceptibility. They also found
correlations between asphalt tenderness, percent asphaltenes and %LMS: high %LMS
was related to high asphaltene contents and non-tender asphalts. Based on this
56
.::: ::;. . ... I , ...... · I
! I
3 ...... . I . . . . . . . .
I , .
..l
' ~--' !
i i
._L~.--.'.--. _1_ '.. ' .i ·r ·········· r· ---! ...... ~
........ 1-
2Z 26 28 30
Figure 23. (LMS)lB.l2S plotted vs LMS.
57
study, there appeared to be desired lower limits of %LMS in asphalts to reduce
asphalt problems associated with tenderness. In view of the considerable data
by Jennings and his co-workers on the relationships between cracking, .. %LMS and
climate, it is likely that, for a given climatic zone, there is an optimum range
of %LMS (or %SMS) for the best pavement performance: too high LMS percentage
causes low-temperature cracking: too low %LMS causes high temperature rutting
and setting (tenderness) problems.
More extensive and systematic correlation tests will be conducted, during
the second phase of this project, between these indices and LMS ratings, as well
as the results of thermal and x-ray analyses.
3,5,3 Thermal analyses: A comparison of the DSC data summarized in Table 8
with each other and the results of other tests shows that the only correlation
that can be pointed out concerns 6H and the source of the sample: 6H values for
original J samples are on the average 24% higher than those for K samples.
The effect of aging on tg and other transformation points, as well as on 6H
appears to be in random directions. Considering that this effect on GPLC
results is unidirectional (see Section 3. 5. 2), it can be argued that the .thermal
effect of the gel to sol transition is overshadowed in thermal analysis by the
larger thermal effect .of dissolution of the crystallized components as treated
by Albert et al. (1985).
3.5.4 X-ray analyses: It appears from the X-ray diffraction spectra and the
Table 9 summarizing these spectra that no regular trend exists in these spectra
regarding the penetration grade or the sample source, nor regarding the effect
of aging. In contrast to what is observed in GPLC, the X-ray spectra are
effected by TFOT in quite a random fashion and direction. The significance and
implications of data in Table 9 will be investigated in Tasks 3-6 when
in-service pavement samples .of known performance information are studied.
58
4. SUMMARY AND CONCLUSIONS
Twelve samples from local asphalt suppliers and their TFOT residues, as
well as six core samples were studied by standard and some specific rheological
0 tests (at +5 C), GPLC, DSC.and X-ray diffraction analysis. The following
conclusions can be drawn from the results of these studies:
(1) Within each viscosity grade of asphalt cements available in Iowa and
meeting AASHTO Specification M226, there were differences in temperature
susceptibility between suppliers and between samples from the same supplier over
time.
(2) Distinctively different GPLC chromatograms were obtained among asphalts of
the same grades, same suppliers and samples supplied at different times.
(3) Distinctively different thermal analysis results and x-ray diffraction
patterns were obtained from asphalts of the same viscosity grades, same
suppliers and samples from the same suppliers but at different times.
(4) Whether and how these differences in physicochemical parameters among
asphalts available in Iowa reflect in mixture properties when they are mixed
with aggregates and in pavement performance under Iowa climatic conditions will
be investigated in Tasks 2 through 6 of this research.
(5) Large differences are observed between samples regarding the
time-dependence of their rheological properties at a low temperature when
brought from a higher or a lower temperature. Especially the strikingly
different and dramatic effect of a cold shock (-30°C) on the properties of the
sample SC-SU (core sample from the surface course of the Sugar Creek project)
might have an important bearing on its poor field performance.
(6) The said dependence appears to be proportionate to their viscosity and LMS
rating, in the case of virgin asphalts.
(7) The elastic modulus may be at least as important as the viscosity to
determine the performance-related low temperature rheology.
59
(8) No decisive correlation is observed between GPLC, DSC and X-ray results.
(9) In contrast to thermal analytic behavior and X-ray diffraction spectra, LMS
rating is found to be unidirectionally sensitive to aging. Hence, it can be
used to monitor or predict aging.
(10) The endothermic peaks on DSC thermograms indicate the presence of
crystallizable components, while the LMS rating measures the presence or
tendency of formation of gels. Therefore, the extent of these peaks (Lili) may be
used to evaluate the low temperature susceptibility of asphalts, together with
their LMS rating. These peaks are on the whole more pronounced in original J
samples than in K samples.
(11) The early-eluted fraction (e.g. (LMS)18.125) in GPLC is found to be a
better measure than the LMS defined by the Montana research group.
(12) Although it is based on a single comparison (Sugar Creek versus Wood
River), the "ageability", i.e. the increase in LMS rating by aging, rather than
the initial LMS rating, appears to be a performance predictor.
5. RESEARCH PLAN IN .TASK 2 (YEAR 2)
Research.in the second year will concentrate on changes in physicochemical
properties of asphalts tested in Task 1 when they are mixed with aggregates in
asphalt concrete mixtures. Asphalt concrete mixtures will be prepared in a
laboratory pugmill mixer using representative Iowa aggregates and asphalts
~ tested in Task 1. These mixes, both before and after artificially aged in
chambers under accelerated environmental conditions, will be tested for Marshall
properties (density, voids, stability and flow), resilient modulus, tensile
strength, stiffness, moisture susceptibility and fatigue life. Asphalts from
these mixes will be extracted and tested as in Task 1.
60
The number, type and sources of aggregates as well as the gradation of the
aggregates and levels of asphalt contents, will be selected in consultation with
the Iowa DOT and county engineers.
In addition, more vigorous investigation for alternative procedures and
data interpretation techniques for HP-GPC work will be undertaken for Task 1
asphalt samples.
6 • ACKNOWLEDGMENTS
This research was sponsored by the Highway Division of the Iowa Department
of Transportation (DOT) under Research Project HR-2.98. This study, under the
same title, was also supported by and designated as Project 1942 of the
Engineering Research Institute, Iowa State University.
The support of this research by the Iowa Highway Research Board and the
Iowa DOT is gratefully acknowledged. The authors wish to extend sincere
appreciation to the engineers of the Iowa DOT, especially Bernie Brown, Vernon
Marks, and Rod Monroe, for their support, cooperation, and counsel. The authors
would also like to thank Gerald Reinke, Koch Asphalt Co.; Alden Bailey, Jebro,
Inc.; Brian Chollar, FHWA; and Joan Pribanic, Montana State University, for
supplying the asphalt samples tested in the study.
The following individuals contributed, in various capacities, to this
investigation: Jerry Amenson, Barbara Hanson, Sang Soo Kim, and Shelley Melcher.
We are indebted to Turgut Demirel for the unselfish giving of his time and
consultation.
61
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14.
a method.of measuring asphalt composition. Research Report FHWA-MT-7930.
Jennings, P. to determine of asphalt.
w. et al. · 1982. Use of high pressure liquid chromatography the effects of additives and fillers on the characteristics Research Report FHW~/MT-82/001.
62
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22. Petersen, J. c. 1984. Chemical composition of asphalt as related to asphalt durability: state of. the art. Transportation Research Record 999:13.
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24. Schmidt, R. J. and L. E. Santucci. 1966. A practical method for determining the glass transition temperature of asphalts and calculation of their low-temperature viscosities~ Proceedings of the Association of Asphalt Paving Technologists, 35:61-90.
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The rheological properties pavement performance. Paving Technologists,
26. Wendlandt, W. Wm. 1986. Thermal Analysis, Wiley., 439-440.
27. Williford, C. L. 1943. X-ray studies of paving asphalts. Texas Engr. Exp. Station Bulletin 73. A & M College of Texas, College Station, Texas.
28. Zakar, P. 1971. Asphalt. Chemical Publishing Co., Inc., New York.
29. Zenewitz, J. A. and Tran, K. T. 1987. A further statistical treatment of the expanded Montana asphalt quality study. Public Roads, 51(3):72-81.
APPENDIX I
HP-GP CROMATOGRAMS
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DSC THERMOGRAMS
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APPENDIX III
X-RAY DIFFRACTION SPECTRA
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Appendix III-1
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