Professional Documents
Culture Documents
net/publication/254314270
CITATIONS READS
27 1,020
3 authors, including:
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Pavel Kriz on 11 February 2014.
ABSTRACT. Major aspects of the glass transition of asphalt binders are described and an
extensive literature review of the phenomenon and its relation to chemical composition is
presented.
The glass transition of asphalt binders was studied by modulated differential scanning
calorimetry and also via dynamic mechanical analysis. A certain analogy between the glass
transition of amorphous polymers and asphalts is suggested. The overall transition was found
to be very broad on the temperature scale.
The effects of evaporation of light-end components and oxidation on asphalt phase stability
and glass transition were studied. It was suggested that phase incompatibility may exist in
asphalts; however, the phase separation is observable after long-term isothermal
conditioning at a temperature within the glass transition range.
Based on the presented results, it is suggested that phase incompatibility develops if there is a
discontinuity in the molecular distribution. Such discontinuity may be present in some neat
binders as well as in severely oxidized or aged asphalt binders.
KEYWORDS: glass transition, modulated differential scanning calorimetry, asphalt binder,
molecular mobility, physical aging, oxidative aging.
1. Introduction
The glass transition is, perhaps, the most important factor that determines the
viscoelastic properties of amorphous material (Williams et al., 1955, Ngai, 2004). It
is a reversible change in an amorphous domain from a viscous or rubbery state to a
hard and relatively brittle glassy state, and vice versa. The glass transition occurs
when the characteristic time of molecular motions responsible for structural
rearrangements becomes longer than the timescale of the experiment. The timescale
for structural relaxation increases rapidly with decreasing temperature (Moynihan,
1994). Therefore, the glass transition is usually considered as a predominantly rate
and non-equilibrium phenomenon.
The transition to a glassy state is accompanied by a sudden change in the
mechanical, optical and thermodynamic properties of the material. The increase in
viscosity is enormous (up to 1013 Pa.s). The material becomes glossy in appearance
and extremely brittle and rigid. The thermodynamic change during the glass
transition upon cooling is recognized as the stepwise drop in heat capacity and loss
in free volume (Ngai, 2004). Note, that the free volume is not a real volume
measurable in cm3/g, but an operational quantity dealing with the molecular mobility
(Struik, 1991).
The glass transition temperature (Tg) is the temperature arbitrarily chosen to
represent the temperature range over which the glass transition takes place: it is
usually assigned to the temperature where half of the sample is already vitrified or
devitrified (Wunderlich, 1994).
In the current study, the glass transition of asphalt is thoroughly described and
investigated by two techniques – modulated differential scanning calorimetry
(MDSC) and dynamic mechanical analysis (DMA). The similarities between the
glass transition of amorphous polymer and asphalt are suggested.
2. Background
decreases with decreasing ring size (molecular weight), as the rings become tighter
and tighter.
2.3.4. Crystallinity
Some asphalts may contain a certain amount of crystalline phase (Claudy et al.,
1992); therefore, the effect of crystallinity on Tg should be also considered. Tg of
amorphous phase may increase as well as decrease with the degree of crystallinity,
depending on the relative density of the crystalline and amorphous phases. In most
cases, the ordered crystalline phase possesses higher density; and, the molecular
chains of the amorphous phase are entrapped in the crystalline lattice. Their mobility
is reduced, and Tg is increased (Flocke, 1962, Bair, 1994). The effect of crystalline
phase on the glass transition of asphalts was found to be significant (Kriz et al.,
2007a).
2.3.5. Dilution
The solvent power and Tg of the oily phase in asphalt are important factors in the
overall Tg. In polymer science, the effect of diluents to lower or increase Tg is well
known. Dilution with a solvent that has a lower Tg than the original material
decreases Tg of the system. Essentially, solvent with a higher Tg than the original
material increases the resulting Tg (Plazek et al., 1991). Furthermore, there are
solutions in which the mobility of the solvent is increased by the presence of a
polymer whose undiluted Tg is higher than that of the solvent. Free volume theory
cannot explain these unpredictable effects, and the additional concept of inter-
molecular coupling was introduced (Santangelo et al., 1994).
3.1. Instruments
this study. Ultra pure helium (99.999 percent) was used to purge the experimental
cell. The rate was 50 mL/min. Standard hermetic aluminum pans were used for all
experiments. The sample mass was in the range of 7-10 mg. Sample pans were
sealed under nitrogen. The thermal history of the sample, if not stated otherwise,
was deleted prior the experiment. The procedure was as follows. The sample was
heated up to 150°C and underwent isotherm for 15 minutes. The sample was then
quenched to −100°C at a rate of 10°C/minute. The MDSC setup was developed and
evaluated in our other papers (Kriz et al., 2007b, Kriz et al., 2007c). The modulation
amplitude was 2°C; the modulation period, 60 seconds; and, the linear heating rate,
2°C/minute. The typical range was from −100 to 100 or 150°C. The glass transition
temperature was assigned to a temperature where the reversible heat capacity
reached half of the overall change.
1
data obtained from the SHRP Materials Reference Library (Jones, 1993), except for
the Tg determination.
2
AASHTO (American Association of State Highway and Transportation Officials)
MP320 (Asphalt Institute, 1994).
2,3
data acquired from Bituminous Materials Chair at the University of Calgary.
4
UOP (Universal Oil Products) 46-85 method (UOP Inc., 1985).
stored in a freezer to minimize the evaporation and to ensure the same number of re-
heatings for each sample. The purging gas was either nitrogen (non-oxidative
evaporation) or air (oxidation) at a flow rate of 60 mL/min. The heating rate was
20°C/min (from ambient to test temperature), and test temperatures varied between
60 and 200°C, depending on the experiment. The sample was held at the test
temperature for 50-1440 minutes.
Four different asphalts were used in this study. Asphalt A was an asphalt from
heavy Alberta crude oil (Cold Lake) of penetration grade 150/200, supplied by
Husky Energy Inc. It represented a high-quality binder for low-temperature
application. Asphalt B was an asphalt from Ural crude oil of penetration grade
150/200, supplied by SLOVNAFT Plc., Slovakia. It represented an asphalt binder
produced from the crude oil typically processed in Central Europe. The other two
binders were Asphalts AAC-1 (Redwater) and AAV (Alaska North Slope) from the
original Strategic Highway Research Program (SHRP) Material Reference Library.
These three binders had been stored in bulk (15kg) at room temperature for 15 years.
log aT = − c1 (T − Tr ) / (c 2 + T − Tr ) [1]
where, c1 and c2 are the empirical fitting parameters, T is the temperature, and Tr is
an arbitrarily selected reference temperature. The frequency where the loss modulus
( G ′′ ) attains its maximum value is usually assigned as the glass transition frequency
(Wada et al., 1959). With the use of tTs, the frequency can be converted to
temperature:
10 Road Materials and Pavements Design. Volume X – No X/2007
ω = aT ω [2]
Tg = Tr +
(
c1 log ω g / ω ) [3]
(
c 2 + log ω / ω g )
where, ω g is the frequency at the maximum of G ′′ , and Tg is the glass transition
temperature. Using Equation 3, the glass transition temperature of the material can
be calculated as a function of testing frequency (Kriz et al., 2008). Results for
Asphalt A are presented in Figure 2.
10
-10
-20
Tg [°C]
-30
-40
-50
-60
-10 -5 0 5 10
log ω [rad/s]
1 10 100
-20
-24
Tg [°C]
-28
The effect of oxidative aging on asphalt phase compatibility and the glass
transition temperature was studied. Asphalt A, which has a negligible crystalline
domain, was chosen for this experiment. The processes associated with the
crystalline phase may not only overlap with the glass transition on the calorimetric
signal, but also contribute to the incompatibility of the amorphous phase (RAPh)
(Kriz et al., 2007a). The absence of the crystalline phase in Asphalt A permitted the
evaluation of the effect of oxidation on phase stability and glass transition. The
reversible calorimetric signal of neat Asphalt A (Figure 5) shows no phase
separation and a uniform amorphous phase. The peak shape suggests a Gaussian
molecular distribution. Each molecule contributes to the glass transition at a
particular temperature based on the molecular weight, structure and inter-molecular
interaction. An irreversible calorimetric signal (not presented) showed a very small
crystalline domain (heat of melting in the order of 0.5 J/g), which was the lowest
value we have ever observed in an asphalt binder. As more than 20 different binders
were subjected to the MDSC experiment in our laboratory, a purely amorphous
binder may be considered as a rarity.
number, but also on the molecular structure (Wessel et al., 1995). The heavy oil
distilled from asphalt consists predominantly of saturates (~50%) and naphthene-
aromatics (~40%) (Noel et al., 1970). Single bonds in saturated molecules possess a
rotational degree of freedom; and, a whole chain is, therefore, more flexible than in
molecules with multiple bonds or rings. Higher molecular mobility of saturated
molecules results in a lower Tg (Ngai, 2004), and removal of such a component
essentially leads to an increase in overall Tg.
262
y (●) = 0.66x + 247.02
260 R2 = 0.99
258
y (▲) = 0.66x + 246.75
256 R2 = 0.98
Tg [K]
254
The results obtained for Asphalt A (Figures 6 and 7) were consistent with the
literature, where Tg was already found to increase linearly with the decrease in
penetration (du Bois, 1966) or the logarithm of penetration (Schmidt et al., 1965). It
has also been found by several researchers that the overall Tg linearly increases with
the amount of mass fraction of asphaltenes, the heaviest asphalt fraction (Wada et
al., 1960, Giavarini, 1984). The simple linear behavior of Tg upon evaporation
(Figure 6) suggests that the raise in overall Tg was directed predominantly by a loss
of the “low Tgi” component. No separate glass transition outside the main transition
was observed in the neat Asphalt A (Figure 5). The solubility factor plays an
important role during the glass transition. The heaviest and most polar molecules
vitrify at much lower temperature than they would normally do as a separate entity,
due to being mobilized and prohibited to pack into a glass by molecules of a much
lower Tg.
Figure 9 presents the reversible calorimetric signal of Asphalt A and its
asphaltenes and maltenes. Asphaltenes were prepared using the American Society
for Testing and Materials’ ASTM D-3279-97 method. The glass transition of
asphaltenes is extremely broad, due to higher molecular weight and variety in
molecular types (see section 4.3.4.). The signal change above 200°C was caused by
the deformation of the pan bottom as the internal pressure increased upon heating.
This was confirmed visually. The asphaltenes and maltenes had glass transition
temperatures of 68 and −30.8°C, respectively. The weight fraction of the asphaltenes
was 12.9 %wt. The glass transition temperature of Asphalt A was calculated from
the glass transition temperatures of the asphaltenes and maltenes, using a simple
mixing rule (Krevelen et al., 1976). The value of −18.1°C was obtained (original
Asphalt A has Tg of −25.7°C). The difference was expected, as this approach omits
molecular interactions and solubility effects that were present in the original asphalt.
Glass Transition in Asphalt Binders 17
4.3.2.Effect of Oxidation
Asphalt A was oxidized in air at 200 and 275°C. The glass transition temperature
was determined and plotted versus the weight loss. The results are presented in
Figures 6 and 8. An interesting fact was observed: there was only a negligible
difference between the glass transition temperatures of the evaporated (under
nitrogen) and oxidized samples. The glass transition still increased linearly with the
weight loss and the slope, and a y-intercept of the linear fit was not affected by
oxidation. The curves were very similar with a single Gaussian peak in both the
oxidized and evaporated binders, as shown in Figures 7 and 8.
It was expected that oxidation would affect the phase stability of the system and
that a phase separation would set in. This was, however, not observed in samples
with no thermal history. Thermal history turned out to be critical in this phase
stability issue (see section 4.4.).
amorphous domain would be observable only if the associated molecules that form a
new phase still possess some degree of the molecular mobility and, therefore, the
ability to exhibit glass transition. The new phase should be observed as a new peak
on the calorimetric signal. This was not observed (Figures 7 and 8). Second, the
molecules forming the new phase have lost molecular motion (associated molecules
may have significantly restricted mobility since they are closely packed and possess
a very low degree of freedom) and now behave like an “immobilized” solid phase.
This phase would have extremely low molecular mobility; and, its glass transition, if
it exists, would be extremely weak and perhaps undetectable in the calorimetric
experiment. In such a case, the removal of the high molecular weight molecules
from the original amorphous phase would lower the glass transition of the remaining
amorphous phase. This is in conflict with the peak broadening and increase in Tg
upon evaporation/oxidation (Figures 7 and 8).
Figures 6-8 indicate that there is no significant difference between oxidized and
evaporated samples in terms of glass transition and Tg. Even the most severely
oxidized sample (275°C in air, 300 min) showed neither phase separation nor the
glass transition temperature deviated from the trend set by the evaporated samples.
It has been shown (Kriz et al., 2007a, Kriz et al., 2007b, Kriz et al., 2008) that
isothermal conditioning at a temperature within the glass transition range affects the
phase distribution and glass transition temperature. The glass transition temperature
was found to increase linearly with the logarithm of conditioning time. The
mechanical properties have also been shown to develop with time. A certain analogy
to the physical aging of amorphous polymers was suggested. The studies indicated
that changes within the amorphous phase at low temperatures are extremely slow, as
the diffusion and molecular mobility are reduced.
Figure 10. Asphalt A conditioned at −20°C for 140 days. Percentage represents a
weight loss of a particular sample during the “evaporation” experiment (200°C in
nitrogen). 0% wt. represents the control sample (conditioned but not evaporated).
Curves vertically shifted.
increased by almost 2°C in the original binder; while in the most oxidized sample
(275°C, 300 min, 10.7 %wt. loss), Tg increased by 16.5°C. The change in Tg upon
conditioning was greater in oxidized samples than in evaporated samples, perhaps
due to the increased content of high Tgi components (carbonyl and sulfonyl
functional groups and higher aromatic content The peak split at −20°C (conditioning
temperature) was observed in severely evaporated and oxidized samples (Figures 10
and 11). Upon isothermal conditioning, phase separation occurred with two glassy
domains, stable above and below the conditioning temperature. This indicates that
the phase stability of the oxidized asphalt was affected, and phase separation
occurred. The origin of the small peak observable at around 4°C in Figures 10 and
11 is not clear. It may represent melting enthalpy of water as frost may develop in
the sample upon long term storage at sub-zero temperature.
Figure 11. Asphalt A conditioned at −20°C for 3,360 hours (140 days). Percentage
represents weight loss of a particular sample during the “oxidation” experiment
(200°C in air). 0% wt. represents the control sample (conditioned but not oxidized).
Curves vertically shifted.
4.5.Thermo-reversibility
It has been shown that the changes in phase distribution and glass transition upon
isothermal conditioning within the glass transition range are fully reversible, if the
thermal history is deleted. This can be achieved by heating the sample to a
sufficiently high temperature (150°C) where the solid structure is
devitrified/melted/disassociate, and asphalt becomes a simple fluid (Kriz et al.,
2007a, Kriz et al., 2008).
Glass Transition in Asphalt Binders 21
-5
Tg [°C] -10
-15
-20
-25
-30
Figure 12. Asphalt A with no thermal history (unfilled symbols) and conditioned
at −20°C for 140 days (filled symbols). Original asphalt (○), evaporated in nitrogen
at 200°C (◊), and oxidized in air at 200°C (□).
The thermal history was deleted in the evaporated and oxidized samples, and
MDSC data were recorded. The comparison of the original MDSC run (prior to
isothermal conditioning) and the MDSC run of the conditioned samples with deleted
thermal history is presented in Figure 13. The results indicate that the effect of
isothermal conditioning was fully reversible, as the specimen was heated up to
150°C. Reversibility indicates that the processes observed in asphalt upon isothermal
conditioning are controlled by changes in molecular mobility, which can be affected
22 Road Materials and Pavements Design. Volume X – No X/2007
The sample conditioned at −20°C started to devitrify upon heating very rapidly.
This suggests that molecules that normally devitrify between −50 and −20°C, were
built into the glassy structure. The structure of the already glassy molecules perhaps
obstructed (spatially or by molecular interaction) the molecular motion of these
molecules, and they eventually “froze” in the structure and became glassy – note the
analogy to the rigid amorphous phase (Kriz et al., 2008). Therefore, upon heating,
the restricted molecules could not devitrify until the “constraining molecules”
devitrified too. The restricted molecules are released instantaneously. This explains
the rapid start of the transition at −20°C (Figure 14, curve (a)).
The sample conditioned at 20°C also showed separation into two phases – one
above and one below the conditioning temperature. In this case, the conditioning
Glass Transition in Asphalt Binders 23
temperature is close to transition end (upon heating) yet within the glass transition
range. Therefore, the glassy domain above the conditioning temperature is very
small.
The phase separation was observed after long-term conditioning at the
temperature within the glass transition range in neat Asphalt B and in the severely
evaporated and oxidized samples of Asphalt A. These asphalts are considered as
phase instable asphalts. Phase separation upon long-term conditioning may be an
indictor of the phase stability of the whole asphalt system. If the binder is phase
stable, separation does not occur at the temperature of conditioning. The stability
may be affected by several processes, as shown in Figure 15.
If any disturbance occurs within the sensitive region, as indicated in Figure 15, a
phase separation may occur. With evaporation, the sensitive region is affected only
if significant fraction of light-end components is evaporated. Polar molecules are
sensitive to oxidation, and their polarity is increased during oxidation. Less polar
molecules are not easily oxidized, and their polarity is not significantly affected.
Gradual transition is discontinued, and phase separation may occur. In thermal
cracking, severe treatment at high temperatures leads to a cleavage of covalent
bonds and results in a low boiling product (polarity decreased) and coke (carbonized
residuum). With solvent recovery, the action of non-polar solvent affects the
continuum within the sensitive region and allows the most polar molecules to
associate: phase separation occurs.
Figure 15. Asphalt as a molecular continuum and the effect of 4 processes on phase
stability. Shades of grey represent molecular continuity in polarity or molecular
weight (white - non-polar or lightest, black - most polar or heaviest). The region
between white dashed lines represents the sensitive region, where molecular
continuity is essential for system stability.
As previously discussed, the phase compatible asphalt shows a single Gaussian
peak on calorimetric signal as the glass transition smoothly proceeds from the most
24 Road Materials and Pavements Design. Volume X – No X/2007
mobile to least mobile molecules or molecular chains. In such asphalt, the molecular
continuity from the lightest to heaviest molecules must exist. If it is broken, sooner
or later the phase incompatibility will occur in the asphalt. This material will behave
as a composite material with properties directed by a “weaker” constituent.
5. Conclusions
Acknowledgements
The authors would like to acknowledge the Natural Sciences and Engineering
Research Council of Canada and Husky Energy Inc. for financial support, and the
Bituminous Materials Chair at the University of Calgary for providing the
performance grades for Asphalts A and B.
6. Bibliography
Katz D.L., Beu K.E., “Nature of Asphaltic Substances”, Ind Eng Chem, Vol. 37,
No. 2, 1945, p. 195-200.
Kemp G.R., Predoehl N.H., “A Comparison of Field and Laboratory
Environments on Asphalt Durablity”, Asphalt Paving Technology, 1981, p. 492-537.
Koots J.A., Speight J.G., “Relation of Petroleum Resins to Asphaltenes”, Fuel,
Vol. 54, No. 3, 1975, p. 179-184.
Krevelen D.W., Hoftyzer P.H., Properties of polymers, their estimation and
correlation with chemical structure, Elsevier Scientific Pub. Co, Amsterdam, 1976.
Kriz P., Stastna J., Zanzotto L., “Physical Aging in Semi-Crystalline Asphalt
Binders”, accepted by the 2008 AAPT Annual Meeting and Technical Sessions, April
27-30, 2008, Philadelphia, PA, 2008.
Kriz P., Stastna J., Zanzotto L., “Effect of Low-Temperature Isothermal
Conditioning on Glass Transition in Asphalt Binders”, Proceedings of the 52nd
Annual Conference of the Canadian Technical Asphalt Association, Niagara Falls,
ON, Canada, 2007a.
Kriz P., Stastna J., Zanzotto L., “A Calorimetric Study of the Low-Temperature
Properties of Asphalt Binders”, Proceedings of the 43rd International Petroleum
Conference, September 24-26, 2007, Bratislava, Slovakia, 2007b.
Kriz P., Stastna J., Zanzotto L., “Time Dependence of Asphalt Properties at Low
Temperatures”, The 6th International Symposium on Asphalt Binder Rheology and
Pavement Performance, April 2-3, 2007, Tampa Bay, FL, USA, 2007c.
Mack C., “Colloid Chemistry of Asphalts”, J Phys Chem-US, Vol. 36, 1932, p.
2901-2914.
Masson J.F., Collins P., Polomark G., “Steric hardening and the ordering of
asphaltenes in bitumen”, Energ Fuel, Vol. 19, No. 1, 2005a, p. 120-122.
Masson J.F., Leblond V., Margeson J., “Bitumen morphologies by phase-
detection atomic force microscopy”, J Microsc-Oxford, Vol. 221, 2006a, p. 17-29.
Masson J.F., Polomark G., Collins P., “Glass Transitions and Amorphous Phases
in SBS-bitumen Blends”, Thermochim Acta, Vol. 436, No. 1-2, 2005b, p. 96-100.
Masson J.F., Polomark G.M., “Bitumen Microstructure by Modulated
Differential Scanning Calorimetry”, Thermochim Acta, Vol. 374, No. 2, 2001, p.
105-114.
Masson J.F., Polomark G.M., Bundalo-Perc S., Collins P., “Melting and glass
transitions in paraffinic and naphthenic oils”, Thermochim Acta, Vol. 440, No. 2,
2006b, p. 132-140.
28 Road Materials and Pavements Design. Volume X – No X/2007