H. E.

Schweyer 1

Glass Transition .of Asphalts Under Pressure

REFERENCE: Sehweyer, H. E., "Glass Transition of Asphalts
Under Pressure," Journal of Testing and Evaluation, JTEVA,
Vol. 2, No. 1, Jan. 1974, pp. 50-56.
ABSTRACT: A study was made of the glass transition phenomena
on 28 different types of asphalts by means of a simple dilatometrlc
procedure. The study was made over a range of pressures from
1 atm pressure up to approximately 2000 atm in some instances.
A study of the pressure susceptibility of the asphalt glass transition
temperature demonstrated that there is a linear relationship
between the glass transition temperature and the pressure. The slope
of this relationship was evaluated as the pressure sensitivity of the
asphalt. Data are also presented on the viscosity of certain asphalts
at temperatures of 10 to 60°C under 500 atm pressure. From plots
of viscosity temperature data the viscosity at the glass transition
temperature under 1 arm and 500 arm are compared, It was found
for many of the asphalt studies that the viscosity at the glass transi-
tion was approximately 109 poises for estimates at both 1 and
500 atm absolute pressures.
KEY WORDS: asphalts, glass transition temperature, viscosity,
pressure, bitumens
Asphalt, a high molecular weight material which is amorphous
in character, in general does not exhibit true melting point
phenomena when it is cooled to temperatures where it i s gen-
erally considered to be a solid. However, it does undergo certain
transition phenomena at low temperatures as evidenced by very
rapid changes in viscosity and volume. These changes have
intrigued numerous investigators in an effort to develop infor-
mation concerning the difference in behavior of certain asphalts
in these transition regions. In most cases the research is an appli-
cation of similar studies made for polymers, where considerably
more information regarding the composition is available to
explain the results that are obtained. The phenomenological
results obtained with asphalts are somewhat similar to those
obtained with polymers and, accordingly, the techniques that
have been used with the latter may be applied to asphalt. In
general, the results of such studies have been interesting and
informative. In particular, the application of the Williams-
Landel-Ferry (WLF) relationship [1] has been found to be of
great interest to research investigators in this area. Among the
more recent studies are those of Dobson [2], Schmidt and
Santucei [3], Ling [~], Shoot, Majidzadeh, and Schweyer [5], and
Jongepier and Kuilman [6]. The reference list of these articles
will provide the interested reader with additional sources of
research on this subject. Very comprehensive treatments of glass
transition phenomena have been reported by Shen and Eisenberg
[7] and Ferry [8]. Majidzadeh and Schweyer [9] have presented
some material on free volume considerations for asphalts.
Busot [10] studied the dynamic compressibility of certain
asphalts in the "glassy" region with respect to their recoil and
relaxation behavior.
For the most part the investigations of glass transition phe-
nomena have taken the form of making dilatometric measure-
ments of changes in the volume of asphalts, as the temperature
increases from the relatively low temperature at a constant rate,
and observing the point at which rapid changes occur. As an
alternative to dilatometrie measurements, certain rapid decrease
in viscosity or consistency has been observed during uniform
heating to evaluate the glass transition phenomena point. From
studies of data such as those illustrated in Fig. 1 for dilatometry,
the influence of the rate of heating and other hysteresis effects,
which depend upon whether heating or cooling is employed, can
be shown.
In the ease of heating from a preeooled condition in the solid
state, the material will show the typical slow, and then rapid,
increase in the thermal expansion coefficient of Curve A with a
glass transition temperature Tg shown as the intersection of the
tangents of the two parts of the curve. If a faster rate of heating
is employed, the relative position might be increased somewhat,
but for polymers the effect is not very sensitive to heating rate.
Other phenomenological behavior of interest are the changes
in properties in the "far transition" regions when an amorphorus
material is subjected to strain with intermittent relaxation, as
diagrammed in Fig. 2 patterned after AIdonis, MacKnight, and
Shen [11]. The point of inflection at a modulus value of 10 °
dynes/cm 2 (10 s Pa) has been suggested as the inflection tem-
perature for polymers. For glass-forming materials, the tempera-
tures at which the zero shear rate viscosity has a value of
10 la poises (1018 Pa-s) has been suggested as the glass transition
temperature [7]. (The studies here on asphalt relate to higher
temperatures in the "near transition" temperature range.)
/ / ,I

Presented at the 76th Annual Meeting of the American Society for

Testing and Materials, Philadelphia, Pa., 27 June 1973.
x Professor, Department of Chemical Engineering, University of
Florida, Gainesville, Fla. 32601. FIG. I--Idealized isobaric transition effects,
50

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SCHWEYER ON GLASS TRANSITION OF ASPHALTS ~1

~LmSY

~ ~ ....................
1 RUBBERY ~ ¥15COELASTC
I
I
GLASSYSTATE [
I \ ,~o,o I
T~
TEMP
ERATUE
P, ABSOLUTETEMPERA?ORE,t

FIG. 3--Free volume concepts of Eq 1 after 8hen and Eisenbero [7].

FIG. 2--Generalized deformation reoions for amorphous materials.

An equation relating viscosity at x compared to that at any

However, Ferry [8] has indicated that comparison of mechanical
reference state r may be written as
behavior with volumetric changes at these temperature levels
may lead to ambiguities. ln(nJ,r) = B[(Vo/VA~ - (Vo/V~)r] (3)
It should be noted here that polymers may show more than one
or
transition region. Further, many property changes such as those
for specific heat, enthalpy, activation energy in viscoelastic flow, ln(,x/,,) = B ( 1 / f , - 1/f,) (4)
dielectric loss, and others, may become significant at the transi-
tion region. where f is fractional free volume equal to V I / ( V t + Vo) and =
( V / V o ) near the glass transition where VI is small relative to Vo.
Some Theories on Glass Transition Phenomena Thus, if a/is the rate of temperature induced expansion of frac-
tional free volume (the difference in expansion coefficients ag and
Certain investigators, among whom were Fox and Flory [12], ar of Fig. 3) and if & is the corresponding rate of pressure induced
employed concepts of free volume changes as a reasonable ex- compression, then
planation of the phenomena that cause great differences in the
rates of expansion (dilatometry) or in the viscosity (rheological f r . e = f , + a f ( T - T,) - aI(P - P,) (5)
approach) in the regions below and above the glass transition
Based on Goldstein [15], the effect of free volume changes on
point. Diagrammatically, their analysis is shown in Fig. 3, where
relative viscosities as a function of temperature and pressure
the free volume is considered constant below the glass transition
changes may be used to modify Eq 4 as follows:
temperature and its changes contribute to volumetric changes
only above the glass transition temperature Tg. fit-- fi -- a~(T -- Tr) + t~(P -- P,)]
The relationship is expressed for the total volume as log(,n%p/,r) = [B/(2.303f,) f , + a1(T -- Tr) -- ~s(P -- P,)

V = V[ + Vo = V] + (Vo' + aoTo) (1) and

where: fAT -- (~/a~) ap]
Vs is the free volume, log (~r.e/~r) = -- [B/(2.303 fi)] f r / a / + A T -- (#f/al) A P (6)
Vo is the occupied volume which equals a hypothetical glass
volume, V~', at zero (absolute) temperature plus the It will be observed under isobaric conditions for a p = 0, that
increase in volume in the glass state, agTo, Eq 6 is of the form:
ag is the coefficient of expansion for the glass, and - [B/(2.303 fi)] A T -CIAT
T is the absolute temperature. log (nr.e/~,), = fr/a/ + A T -- C~ + AT (7)
Simha and Havlik [13] proposed that the free volume con- The B is this equation was evaluated by Majidzadeh and
stitutes about 11.3 percent of the total volume at the glass Schweyer [9] for eight asphalts using viscosities at a power input
transition temperature as shown on the diagram. Others [7] have of 1000 ergs/s-em ~ where fi = 0.025 and a] = 4.8 X 10-4 deg -i
arrived at a different value depending upon how free volume is with values varying from 0.956 to 1.002. The calculated vis-
defined. A commonly accepted value is 2.5 percent. cosities at a glass transition temperature for the constant power
Doolittle [I~] proposed an empirical equation for viscosity, 7, input were reported at approximately 10 tetrapoises (1013 poises
related to free volume as follows: or 10 ~ Pa-s). It will be observed that Eq 7 is the same form for
relative viscosities evaluated at zero shear rates for polymers in
= AeCBVotV/) (2)
the WLF [1] equation.
where:
,~rT~p~ I -C~AT -8.86aT
e is the exponential function, logar = l o g ~ l ; _ o - C~+AT- 101.6+AT (8)
A and B are constants, and
Vo and ITs are occupied and free volume, respectively. where ar is the shift factor from superposition analysis.

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52
It might also be noted that the ratios of 5/a in Eq 7 correspond
approximately to the rate of change of glass transition tempera-
ture with pressure (~TJ~)P), which is evaluated in the present
paper as the slope m of Eq 9.
Shen and Eisenberg [7] also review proposed kinetic theories
and the thermodynamic approaches, and present a unifying
theory of their own. Of these only one kinetic theory approach
will be given because it is applicable to certain experimental
work presented here.
The Williams-Landel-Ferry (WLF) relationship [1] has found
considerable acceptance in asphalt technology as was noted
earlier. Although originally empirical in nature, there is some
theoretical basis for the relationship as was considered above in
the comments on Doolittle's contribution. The rheological
aspects of the WLF analysis are also related to rearrangements
of molecules and changes in volume. These rearrangements axe
rate-controlled and affect glass transition phenomena. The
stress-strain, relaxation, and other material properties are also
interrelated with the rates of cooling and heating in observable
glass transition experiments. The inflection point of Fig. 3
reflects such interaction.
In the past the general research on the application of the WLF
equation and glass transition phenomena for the usual asphalt
cements has been studied at atmospheric pressure. Ling [$] made
an expanded investigation of some of the work that had been
done previously by Shoor et al [5] and studied a variety of
different types of asphalts from synthetic to roofing type ma-
terials, in order to provide an expanded range of data as reported
in Fig. 4. In addition, he also used the Arrhenius equation to
evaluate the general temperature susceptibility effect. In fact the
principal contribution of the WLF equation to asphalt rheology
is its generaIization of temperature suseeptibiIity. Other recent
studies in the University of Florida Asphalt Laboratory on the
effect of pressure, raised the question as to how pressure would
affect the glass transition temperature. Moore investigated this
effect in a graduate study at the University of Florida to pro-
vide some of the data for the present paper.
'\' • , • ' ..........
\ \ .....
-30
(T Tr), "C
-
FIG. 4---Generalized shaftfactor for asphalts after Ling [5].
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JOURNAL OF TESTING AND EVALUATION
AIRCYL__NOER
_OOTLETI
P,STON1 [ DIAL
PLUNGER
STEELFRAME/
, ",,,
3/8" ID TUBE U SAMPLE
2" LENGTH
TEMPERATURE •
I
PROBE~ CAP
TORECORDER
FIG. 5---~chematic of isobaric transition apparatus.
Apparatus and Procedure
The method that was employed in the present study consisted
quite simply of using a dilatometrie procedure under conditions
of heating at a fixed rate of l°C/min with a superimposed pres-
sure maintained at different constant values. This isobaric
method was employed for a variety of asphalts used for paving
and roofing. The samples were precooled to about -40°C below
their transition points with liquid nitrogen in an environmental
chamber and then warmed at a constant rate. Good repeata-
bility was obtained.
The apparatus itself is shown in schematic diagram in Fig. 5,
and photographs of the assembly and the components are shown
in Figs. 6 and 7, respectively. Compressed nitrogen was em-
ployed to maintain the constant pressure on the device as the
temperature was raised with a small leak in the system in order
to permit the material to expand under a constant pressure
environment. Isobaric measurements for at least three, and
usually four, different pressures were used in order to define the
relationship between the glass transition temperature and the
imposed pressure. Results are shown for typical isobaric runs in
Figs. 8 and 9. Also, certain asphalts were run by the penetration
method of Shoor et al [5], which is a pseudorheological procedure.
That method generally gave results at 1 arm absolute pressure
in a range of -*-5°C for those of the isobaric method reported in
Table 1.
In addition to these isobaric runs, certain asphalts were run at
specified pressures with an isothermal technique. The air cylinder
of Fig. 5 was replaced with a load cell and the material sub-
jected to an initial pressure of about 2000 atm (30,000 psi) in an
Instron assembly with an environmental chamber at 10°C. The
pressure was then released by moving the plunger upward at a
constant rate of 0.02 in. (.5 mm)/min. The change in load result-
ing from the expansion was continuously recorded and, from the
tracing, the isothermal gtsss transition pressure was determined.
Comparative data at 10°C indicated quite good agreement with
SCHWEYER ON GLASS TRANSITION OF ASPHALTS
FIG. 6---Assembled apparatus.
FIG. 7--Apparatus components.
the isobaric results ( 4-4 percent variation of the mean value) for
five out of six asphalts. It is thought that the one poor agreement
could be improved by repeating the runs. The isothermal pres-
sure changes do not show the rapid changes found in the isobaric
method, so the latter is the preferred procedure. A definite
hysteresis effect for compression versus expansion also was
found for the isothermal method.
Discussion o f Results
The results for typical asphalts, which indicate the linearity
of the relationship between the glass transition temperature and
the glass transition pressure, are shown in Fig. 9. The latter is
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53
a,c.; i
I
! o.o~
0,02
z//
N
e_4o -30 -20 -tO TB 0 l0 20 30
TEi~ERATURE.o¢
FIG. 8--Isobaric transition profiles for an asphalt.
lar~
FIG. 9--Pressure transition profiles.
defined as that pressure required to produce the glass transition
phenomena at a given temperature. It is reported as the pressure
read from a chart at the selected temperature as shown in Fig. 9.
Although not shown, the reproducibility of the method ap-
peared to be quite satisfactory. In most cases the lines for
different runs using three and four points (as in Fig. 9) would
show good agreement. In other cases there was a scattering of
data which was attributed to experimental error.
All of the results reported here are for a heating rate of
l°C/min. This was a most convenient rate for the apparatus
and procedure employed and gave reproducible results.
It is also of interest to note that limited experiments for one
asphalt sample poured and held for 3 days (and probably more)
before testing indicated that after aging the results under
pressure were similar to those tested without aging.
The Pressure Effect on Glass Transition Temperature
As apparent from Fig. 9, there is a linear relationship between
the glass transition temperature and the pressure for asphalts of
the form, in °C,
Tgp -- Tgi -~- m ( P - 1) (9)
where Tgp is the glass transition temperature at any absolute
pressure P in atmospheres, and m is the pressure sensitivity
and the slope of the plots in Fig. 9.
The values of Tal and m for a variety of asphalts are given in
Table 1, and it is quite obvious that they differ greatly for both
sensitivity and absolute value of the glass transition tempera-
ture when different kinds of asphalts and pressures are con-
sidered. The order is the same magnitude as that reported by
54 JOURNAL OF TESTING AND EVALUATION

TABLE 1--Data on asphalts studied.

Rheology, 25°C - Glass Transition Data. T~, °C

V60
Penetration, Complex Flow Viscosity, 140°F
Asphalt 25°C Index, C Megapoises KP b 1 atm~ Sensitivity,~ m 500 atm

1. Air Blown 88 0.78 1.05 1.72 --7.0 0.030 8.0

2. Venezuelan B 85 0.80 1.12 3.07 --4.5 0.031 12.0
3. Californian A 91 1.02 0.875 0. 930 1.0 0. 033 16.5
4. Air Blown 84 0.87 1.26 1.25 --2.0 0.029 12.5
5. Mixed 87 9.76 1.00 2.11 --9.0 0.032 7.0
6. Venesuelan A 62 0.85 2.23 3.04 2.2 0.015~ 11.3
7. Venezuelan B 54 0.83 3.66 6.00 1.6 0.017 10.0
8. Venezuelan B 91 0.83 0.90 2.27 --8.4 0.032 7.6
9. Canadian A 92 0.99 0.91 0. 708 1.4 0.019, 9.6
10. Californian A 88 0.97 1.43 1.34 --1.4 0.023~ 13.1
11. Low Asphaltene 79 1.01 2.48 1.84 --1.7 0.017 7.0
12. Air Blown 73 0.68 1.10 3.11 --9.1 0.022, 2.4
13. Air Blown 89 0.65 0. 972 2.50 --5.0 0.026* 8.0
14. Air Blown 34 0.74 9.40 21.8 --1.1 0.021 9.4
15. Roof Asphalt 33 0.58 0.g73 40.4 1.1 0.015 6.2
16. Air Blown 25 0.28 8.49 --0.3 0.009 4.2
17. BPR-B3056 26 0.88, 12.9, 1~:66 6.8 0.021, 17.9
18. BPR-B3057 19 0.74 45.4 5.55 1.5 0.046, 24.5
19. Roof Asphalt 22 0.44 22.6 272 --4.2 0.029 10.5
20. Low Asphaltenes 147 1.04 0. 339 0.95 --5.5 0.024 6.3
21. Air Blown 158 1.08 0. 226 0.737 --8.6 0.037 6.7
22. Kansas 87 0.78 t. 08 1.69 --9.4 0.023 2.2
23. Mexican 89 0.81 1.69 4.50 -10 0.038 9.2
24. BPR-B3053 43 0.83 3.88 6.82 -2.5 0.020 7.5
25. Californian B 77 0.92 1.40 1.10 --7.8 0.057, 20.6
26. SR Gulf Coast 85 0.90 1.17 1.70 --8.6 0.034 8.3
27. Shale Oil 93 1.12 5.68 0.82 0.6 0.026 13.6
28. W. Texas soft 0.98 0. 258 0.413 --3.6 0.027 10.0

Measured at constant power input of l0 s ergs/s-cm 8 in regular Florida capillary method (latest corrected data).
Cannon-Manning, except No. 19 which was with Florida capillary at :~ = 1.
By extrapolation or direct measurement in pressure apparatus.
d Slope of glass transition profile, °C/arm.
* Average of two or more runs.

F e r r y [8] for polymers. Bianchi [16] reports values of ( d T J d P )

from 0.015 to 0.037, depending upon the experimental procedure lo9

using three different methods for two polymers. 0 ' R e i l l y [17] m

discusses the fJs/,~z ratio. H e reports values of d T ~ / d P of 0.004 to
~'°'I
0.044 for such diverse materials as glycerol and Lexan poly- i lo
carbonate; c o m m o n polymers showed values of about 0.024. lo5
Figure 9 demonstrates t h e v e r y i m p o r t a n t concept t h a t t h e e~ssu~l All~jO
lo4
glass state cannot be described by t e m p e r a t u r e or pressure alone. t~. Iso •
NO. 2 2 ~ &
There is either a glass transition temperature Tg and a corre-
sponding value of pressure P or there is a glass transition o 40 eo sO ~e ~ ~

pressure Pg with a corresponding t e m p e r a t u r e T. The state

diagram (or E q 9) is necessary to describe the interdependence
of the two state variables.
Studies of Viscosity in the Transition Region
As indicated in Fig. 2, t h e deformation characteristics of
amorphorus materials in the far transition region m a y be quite
complex. Furthermore, studies under pressure add complications
to the temperature effects because of a shifting of the transition
regions to higher t e m p e r a t u r e levels. R e c e n t investigations
reported b y Lodge [18] provided a technique for studying the
pressure effect on viscosity of certain of the asphalts in the near
transition range. D a t a were run at 10, 25, and 60°C with vis-
cosity results reported at 1 and 500 arm (7335 psig) pressure as
shown in Table 2.
Typical viscosity d a t a are plotted in Fig. 10 on the A S T M
D 2493 (Viscosity-Temperature C h a r t for Asphalts) plot for
viscosities, at a standard rate of shear of one reciprocal second
FIG. lO--Pre~sur~temperatur~cod~y ~ r ~ .
(~ = 1) and pressures of 1 and 500 arm. I n general, the d a t a
indicate essentially linear relationships. However, in view of the
expected behavior shown in Fig. 2, it is expected t h a t some
curvature and flattening of the curves will be shown as the
glassy state is induced in asphalts.
The smaller slope of the asphalt viscosity-temperature lines as
the pressure is raised results in intersection of the plots, which
probably has further significance relative to glassy behavior. I t •
would be expected t h a t pressure effects in the glassy state would
become less significant since the molecules under these conditions
h a v e less freedom for rearrangements.
Since the viscosities at glass transition temperatures for 1 and
500 arm pressures were available for a n u m b e r of t h e asphalts, it

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 SCHWEYER ON GLASS TRANSfflON OF ASPHALTS 55

TABLE 2~--Rheo/og/ca/datafrom pressure viscometvr r u n s . *

At 10°C (50°F) At 25°C (77°F) At 60°C (140°F)

Complex 71.1 ~990,~ Complex m.t ~50o,z Complex ~z,l ,909.~ ~m
Penetration Flow, C MP MP Flow, C MP MP Flow, C KP KP KP

10 89 0.90 12.4 268 0.94 1.84 19.7 0.96 2.01 37.2 1.34
11 72 0.65 35.5 429 0.68 0.709 22.2 0.91 2.80 36.0 1.84
12 73 0.62 8.02 164 0.56 0.55 3.79 0.83 4.00 21.3 3.11
13 89 0.63 8.10 88.0 0.69 0.730 7.28 0.79 4.19 41.4 2.50
15 33 0.39 30.0 117 0.57 3.30 18.9 0.70 29.9 247 40.4
16 25 0.29 8.85 29.1 0.38 2.28 5.60 0.27 135 392
17 26 0.45 36.2 457 0.65 O. 65 31.5 0.87 6.75 38.0 3166
18 19 0.44 230 40909 0.83 40.2 231 0.81 14.6 195 5.55
19 22 0.34 56 166 0.57 5.9 25.8 0.48 224 1030 2500
20 147 0.75 10.3 363 0.88 0.382 11.4 0.99 2.00 10.5 0.95
22 87 0.54 8.09 120 0.54 0. 625 55.3 0.88 2.70 25.5 1.69
23 90 0.55 21.1 176 0.74 1.27 14.2 0.97 4.85 52.5 4.50
25 77 0.76 12.2 436 0.60 0.616 20.2 0.91 2.54 30.3 1.10

~AI1 viscosities at 4 = 1 s'1; first subscript number is nominal imposed pressure in atmospheres, absolute; CM is Cannon Manning apparatus in
ASTM D 2171-66.
b At 15°C (59°F).

was possible to compare their glass transition viscosities by Conclusions

extrapolation or interpolation from plots such as Fig. 10, where
The assumptions employed in studying the experimental
the small arrows indicate the estimated values. The available
viscosity and glass transition data herein are: (a) applicability of
numerical results are listed in Table 3.
the power law over the rates of shear studied, (b) uniform power
law coefficient for all pressures as evaluated visually by the best
TABLE 3---Summary of glass transition rheoloFy data.° straight lines, and (c) uniform slopes of pressure susceptibility
relationship for viscosities at all shear rates in the pressure
Glass Transition Data apparatus. These assumptions have been found reasonably
acceptable for the conditions of the experimental work reported
Transition 1 atm 500 atm herein for most regular paving asphalts. However, other types of
Sensitivity,
No. m Tg, K(°F) ,g, GP Tg, K(°F) ~, GP asphalts might give somewhat erratic results. It is believed that
with improved apparatus and more experience most of the
10 0.023 272/29 0.30 286]56 0.20 scattering of data could be reduced. Accordingly, the general
11 0.017 271/29 0.90 280/45 1.3
12 0.022 264/16 0.85 276/37 0.80 conclusions are drawn with the reservation that for certain
13 0. 026 268/23 0.35 281/46 0.16 materials, the above assumptions must be considered as first
15 O.015 274/34 0.17 279/43 0.40 approximations to precise answers.
16 0. 009 273/32 0.03 277/40 0.08
17 0.021 280]44 0.19 291/64 0.10
18 O.046 275/35 50 298/76 0.20 • There appears to be a definite volume transition phe-
19 0. 029 269/24 0.45 284/51 0.13 nomenon shown by asphalts at low temperatures which is
20 0. 024 268/22 0.60 279 [43 1.0 affected by the imposed pressure.
22 0. 023 264/15 6.0 275/36 2.0
23 0. 038 263/15 7.0 282/48 0.40 • The relationship between the empirical transition tempera-
25 0. 057 265/18 1.5 294/69 0.65 ture and the pressure follows a linear relationship up to about
700 arm (10,000 psi) whose constants vary with the material.
GP is in gigapoises (109 poises) for :t at one reciprocal second.
Pressures are in absolute atmospheres. • Some asphalts at their glass transition temperatures and
different pressures showed similar glass transition viscosities
(for rates of shear of one reciprocal second). This was not general,
however, indicating that other parameters also need to be
As indicated in Table 3, there is a similarity of viscosity at the
considered.
respective pressure glass transition points, at a magnitude of
• The quite different behavior of various asphalts in the near
about 1 gigapoise (109 poises). There are also certain discrep-
transition region under pressure further emphasizes the potential
ancies, viz, Asphalts 16, 18, and 23. These differences are attribu-
difficulties associated with prediction of properties in this region
ted to differences in chemical composition and structures for
from data at more elevated temperatures, such as use of the
the asphalt.
penetration index (PI) as proposed by some investigators.
There' are numerous new aspects of glass transition phe-
nomena of polymers that may be applicable to asphalts which
are discussed by Boyer [19]. Also, the reader who is interested in Significance
the thermodynamics of the glass state can refer to 0 ' R e i l l y [17] The results of the effect of pressure on glass transition be-
and to Passaglia and Kevorkian [~0] for discussions. Kaelbe [21] havior and the increase in viscosity provide implications that
has discussed the free volume aspects of polymers in some detail. may be of considerable importance in pavement cracking.

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56
Certainly the effect of pressure in raising the glass transition
temperature of paving asphalts puts them into the temperature
range usually encountered in northern USA and Canadian
climates for much of the year. Further, such temperatures are
reached regularly in Florida and other southern states in the
winter months.
The writer is not knowledgeable as to whether traffic induced
stresses up to 700 atm (10,000 psi) are reached in pavements.
However, it seems reasonable to expect that where high loads are
carried by extremely small areas between aggregate particles
that substantial pressures could be attained. Furthermore,
asphalt is permeable to water vapor. When the temperature is
lowered this vapor can condense and upon freezing with in-
creased volume, the resulting ice could develop very high
pressures. One might hypothesize that such conditions under
traffic could initiate cracking a t temperature ranges below
0°C (32°F).
Other potential conditions t h a t might induce high stresses are
the settling of land fills where the base support area is weakened,
thereby permitting high stresses to develop in the hinder course
of surface course layers, and similarly hydraulic pumping of the
sublayers where drainage problems produce weakened base
layers. Earthquakes a n d / o r other land movements of a minor
nature perhaps could produce high stresses in the surface layers.
The development of potholes of a size such that wheel contacts
at the forward edge of the hole produce shock waves in the
surface layers might develop substantial stresses. All of the
above conditions might produce incipient cracking.
The initial cracking of asphaltic concrete highway pavements
is an indicator of probable future deterioration and highway
failure. As such it is a precursor of future maintenance and
possible highway replacement with attendant expenditures and,
therefore, its causes are of great interest to highway engineers.
Cracking apparently is initiated by a large number of condi-
tions, some of which are environmental (climatic or imposed),
some of which are caused by material properties, and some of
which are the result of poor design. It was the purpose of this
paper to discuss certain properties of the bituminous component
of asphaltic concrete which m a y be of importance in cracking
considerations.
When asphalt is subjected to stress it must deform or fail;
when it deforms there may be certain associated volumetric
changes. If the asphaltic bitumen cannot accommodate the
stress-strain volume requirements, it will exceed its cohesive
properties and develop cracks. The glassiness behavior exhibited
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by many asphalts at the lower ambient temperatures m a y be
directly associated with the cracking phenomenon. This de-
duction is based upon consideration of the volume-rate changes
associated with temperature changes and imposed pressures.
Accordingly, glass transition phenomena for asphalts under
pressure should be of interest to asphalt technologists concerned
with cracking.
Acknowledgment
Acknowledgment is made of the support of the National
Science Foundation through grant GK-19467 for carrying out
this research. The author is grateful for the assistance of F. Kafka
and D. Bowden in helping to analyze the experimental data, and
for the help of J. Kalway in constructing certain apparatus
components.
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