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org/journal/ascecg Research Article

Effects of Elemental Sulfur on the Aging Trajectory and Adhesion

Characteristics of Rubber-Modified Bitumen
Albert Hung, Mingxia Li, and Elham H. Fini*
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ABSTRACT: This study examines the role of sulfur in rubber-

modified bitumen and its response to ultraviolet (UV) exposure in
terms of its viscoelasticity, creep recovery, healing behavior, surface
chemical oxidation, and surface adhesion. Infrared spectroscopy
showed a pronounced enrichment of oxidized sulfur and carbon
compounds at the surface of sulfur-modified bitumen after mild
heating and especially after UV irradiation. 3% added sulfur increased
bitumen plasticity by all measures. UV aging marginally decreased bulk
metrics of self-healing, but it severely diminished surface adhesion
values, indicating that bulk metrics may not be able to accurately
reflect crack-healing behavior if bitumen surfaces are prone to
oxidative degradation.

KEYWORDS: Bitumen, Asphalt, Sulfur, Aging, Oxidation, Healing, UV, FTIR, Rheology

■ INTRODUCTION
Bitumen and elemental sulfur are major byproducts of oil and
gas refining. Bitumen naturally contains 1−7% sulfur depend-
ing on the source of the crude oil and the refining process.1,2
However, because of the reduction in allowable sulfur in
marine fuel by the International Maritime Organization as well
as the development of sulfur-rich oil reserves, there is projected
to be a near-term surplus in sulfur production.3,4 As a result,
many asphalt producers are aiming to add 8−12% elemental
sulfur to bitumen. A separate trend that is also leading to an
increase of sulfur content in bitumen is the use of ground or
liquefied waste tire rubber as a bitumen modifier or extender in
some U.S. states.5,6 The vast majority of refined bitumen is
used as a binder in asphalt concrete for road construction. To
maintain the performance and durability requirements of
pavement construction, it is immediately important to
elucidate the impact that various forms of added sulfur have
on the properties and life cycle of bitumen.
Elemental sulfur has been studied as a bitumen modifier for
several decades either as a rubber compatibilizer7−9 or in
significant fractions (20−50%) as a bitumen extender,3,10−12 to
reduce material cost and crude oil consumption. Smaller
amounts of added elemental sulfur (<15%) tend to plasticize
bitumen and improve low-temperature performance; higher
amounts lead to stiffening, partly because undissolved sulfur
acts as a reinforcing filler.12−15 Studies on sulfur-extended
asphalt (SEA) compared to conventional bitumen show an
increase in stiffness and rutting resistance and mixed results in
fatigue and susceptibility to moisture damage.12,16−21
Fewer studies have investigated the effects of elemental
sulfur on bitumen aging and oxidation, and many of those
studies include comodifiers such as styrene−butadiene-styrene
(SBS) that make direct comparisons between studies more
difficult. Regardless, this is an important topic of research
because sulfoxide groups are involved in age-related hardening
of bitumen.22 Sulfur reacts with bitumen compounds,
especially at high temperatures and high sulfur concen-
trations,23,24 and aliphatic sulfide groups are more likely than
other sulfur groups to oxidize.2 Elemental sulfur typically exists
as stable 8-atom rings (S8), and it is hypothesized that
elemental sulfur is at greatest risk of oxidation when the rings
are opened in either of two ways: cross-linking the sulfur to
rubber chains or bitumen hydrocarbons, or holding the sulfur
at temperatures well above its melting point (119 °C) for
extended periods of time.25 Indeed, SBS-modified bitumen
shows an increased susceptibility to oxidative aging with the
addition of sulfur, as measured by Fourier transform infrared
spectroscopy (FTIR),26 although rheological metrics of aging
are confounded by concurrent degradation of the SBS
modifier.27 By contrast, sulfur added to terminal-blend
rubberized bitumen showed a marginal reduction in age
Received: July 16, 2021
Revised: September 13, 2021
Published: December 3, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c04798

16918 ACS Sustainable Chem. Eng. 2021, 9, 16918−16925
ACS Sustainable Chemistry & Engineering
hardening,28 but the results may be complicated by the fact
that commercial rubber contains antiaging additives.29−31 SEA
showed significant age hardening under laboratory-modeled
long-term aging, although this effect could be mitigated
somewhat by careful selection of the initial bitumen grade
and the sulfur concentration.32
The effect of ultraviolet (UV) exposure on high-sulfur
bitumen is poorly understood. Aliphatic disulfides can be
cleaved by UV light,33 and the resultant sulfur radicals can then
initiate other free-radical chain reactions such as S8 ring
opening, polysulfide chain abstraction, and cross-linking with
hydrocarbons. Pure elemental sulfur is stable under UV
irradiation, but it has been shown to be a weak photocatalyst,
capable of splitting water into reactive radicals.34 Although the
penetration depth of UV light into bitumen is shallow,35 the
physical and chemical effects at the surface can be
extreme.36−39 Even without added sulfur, oxidized sulfate
(SO4) minerals are a large proportion of the nonvolatile
residue left behind after UV degradation of bitumen thin
films.38
In this study, changes in the rheology, surface chemistry, and
surface adhesion of sulfur-modified, rubber-modified bitumen
were measured in response to mild heat treatment or UV
irradiation. Attenuated total reflectance (ATR) FTIR was
sufficiently surface-sensitive to identify oxidative degradation at
the bitumen surface and the resultant chemical products.
Dynamic shear rheometry (DSR) was used to measure the
viscoelasticity, creep recovery, and self-healing ability of the
bulk material. In addition, a custom apparatus to measure the
pull-off force was used to obtain preliminary data on the
surface adhesion of UV-aged samples.
■
EXPERIMENTAL METHODS
Materials. The bituminous asphalt binder used in this study is PG
64-22, obtained from HollyFrontier Corporation in Arizona. General
properties of this binder are listed in Table 1. This brand of binder,
widely used in Arizona, is modified with a proprietary form of
liquefied tire rubber. Reagent-grade sulfur powder was acquired from
Fisher Scientific.
Table 1. General Properties of the PG64-22 Asphalt Binder
Studied
technical index value
specific gravity @ 15.6 °C (g/cm3) 1.041
flash point, Cleveland Open Cup (°C) 335
mass change after RTFO −0.013
absolute viscosity @ 60 °C (Pa·s) 179
Sample Preparation and Aging. The rubber-modified bitumen
was mixed with 3 wt % sulfur at 135 °C for 5 min to make the sulfur-
modified mixture. For surface adhesion and spectroscopic measure-
ments of samples that were not UV-aged, 0.5 g of control bitumen or
sulfur-modified bitumen was drop cast onto glass microscope slides
and annealed on a hot plate at 120 °C for 90 min. This temperature is
less than most compaction temperatures and was not initially
intended to mimic any kind of short-term aging, only to obtain a
smooth, glossy surface. These samples are referred to as “heat
treatment” or “heat only” samples.
To get bitumen samples subjected to UV irradiation, a QUV
accelerated weathering machine (Q-Labs) was used. The UV lamp in
the weathering machine was a UVB-313 EL with a peak illumination
intensity of 0.71 W/m2/nm at 313 nm in a standard configuration. To
make samples for UV aging, 6 g of control bitumen or sulfur-modified
bitumen was evenly spread at 135 °C in a 8 cm diameter silicone
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rubber dish to make a film about 1 mm thick. The dish was placed in
the UV chamber at 65 °C, 10 cm away from the lamp, and subjected
to continuous UV exposure for either 100 or 200 h. Optical
microscope images were captured with a digital USB microscope
(TQC Sheen). Photographs of the samples before and after UV
treatment are shown in Supporting Information, Figure S1.
DSR, Creep, and Healing Tests. The rheological properties of
the bitumen binders were measured with an MCR 302 DSR (Anton
Paar). All tests were performed at 25 °C unless otherwise specified.
The magnitude of the dynamic shear modulus |G*| and the phase
angle δ were measured for a shear-strain level of 0.1%. Three
replicates were measured for each sample.
The multiple stress creep recovery (MSCR) test was used to
determine the creep compliance and recovery in the bitumen mixtures
at two stress levels at 25 °C, in accordance with ASTM D7552-09.40
This test used a different spindle geometry (8 mm parallel plate and 2
mm gap) than the common standard in order to match the healing
index test. For each cycle, the sample was loaded at constant stress for
1 s and then allowed to recover for 9 s. The creep and recovery cycles
were run at 0.1 kPa applied shear stress, followed by 10 cycles at 3.2
kPa. Three replicates each of control bitumen or sulfur-modified
bitumen were measured. For each cycle N at a given applied stress,
the instantaneous strain εi,N at the end of the loading period and the
permanent strain εp,N at the end of the recovery period were collected.
At 0.1 kPa, only the last 10 cycles were counted. The strain values
were used to calculate the nonrecoverable creep compliance Jnr and
the percent deformation recovery R averaged over 10 cycles at each
applied load L = 0.1 or 3.2 kPa based on eqs 1 and 2.
1
Jnr (L) = ⟨εp , N /L⟩N = ∑ εp, N /L
10 N (1)
εi , N − εp , N 1 εi , N − εp , N
R(L) = = ∑
εi , N 10 εi , N
N N (2)
A DSR test was conducted to evaluate the healing capacity of
bitumen mixtures based on an empirical metric that looks at recovery
of |G*| after loading.41−43 This test used the same geometry and test
temperature as the MSCR test and was performed for three replicates
each of control bitumen and sulfur-modified bitumen. Each sample
was sheared at a strain of 5% and a frequency of 10 Hz until |G*| was
reduced to 50% of the initial value. The initial value of the complex
shear modulus before loading is called Go, and the value of the
modulus at 50% of the initial value is called Ga. The shearing was then
stopped, and the sample was given a rest period of 15 min. After the
rest period, the value of the complex shear modulus was measured
and denoted Gb. The healing index HI was calculated using eq 3.41−43
G b − Ga
HI =
Go − Ga (3)
ATR-FTIR. ATR-FTIR was performed on a Nicolet iS50
spectrophotometer (Thermo-Fisher) using the Smart iTX accessory
with a standard diamond ATR crystal. ATR-FTIR is moderately
surface-sensitive; the intensity of the IR evanescent wave decays
exponentially over a decay length of 0.5−4 μm from the diamond−
sample interface. The decay length is also called penetration depth dp
and is calculated by eq 4.
λ
dp =
2π(n12 sin θ − n22)1/2
2
(4)
In eq 4, θ is the internal reflection angle (θ = 45°), n1 is the
refractive index of the diamond crystal (n1 = 2.4), λ is the IR
wavelength, and n2 is the refractive index of the sample.44
Measurement of the surface of the heat-cast sample was performed
by inverting the sample and pressing the exposed surface to the ATR
crystal. Measurement of the bulk material for both heat-cast and UV-
exposed samples involved slicing away a small area of the sample
surface with a precision knife and digging out a portion of the
underlying material (typically from >0.5 mm below the surface) to
https://doi.org/10.1021/acssuschemeng.1c04798
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Figure 1. ATR-FTIR spectra of rubber-modified bitumen (a) control, (b) mixed with 3% elemental sulfur. Spectra were taken of the surface (blue)
and underlying bulk (black) after sample preparation at 120 °C, and of the surface after 100 h (dark red) and 200 h (magenta) UV exposure.
Spectra were normalized to the total absorbance from 3700 to 500 cm−1. Yellow and green arrows highlight peaks of interest.

Figure 2. Chemical structures of various oxidized sulfur groups.

press against the crystal. Measurement of the surface of the UV-

exposed surface was done by extracting a small slice of the surface
(roughly ∼0.5 mm thick), taking care to avoid excessive mechanical
deformation, and pressing the top of the slice to the crystal.
Custom Measurement of Pull-off Force. The surface adhesion
of bitumen samples was measured using an inexpensive in-house
apparatus (see Supporting Information, Figure S2). Before each
measurement, a hemispherical glass cabochon (1 cm diameter,
available from arts-and-crafts suppliers) is cleaned by 5 min UV-ozone
treatment in a SC-UV-I UV-ozone cleaner (Setcas, LLC) and then
equilibrated for 1 h in a 100% humidity chamber. The glass
hemisphere is then attached to light thread and hung from a FGV-
2XY digital force meter (0.01−10 N force range, Nidec-Shimpo
Corp.). The sample is placed on a rigid surface on top of a
compressible foam spring. The sample stage is pushed down by hand,
slid under the force meter, and slowly released so that the sample
gently lifts up into contact with the glass hemisphere. The glass bead
is allowed to rest on the sample surface under its own weight (0.74 ±
0.025 g) for 10 min under ambient laboratory conditions (20 °C,
∼25% relative humidity). The sample is then pushed down relatively
quickly (>5 cm/s) to separate the glass bead from the surface while
limiting viscoelastic effects, and the maximum pull-off force is read
from the force meter. Before UV-ozone cleaning and reuse, trace
bitumen is removed from the surface of the glass cabochon by wiping
it with acetone and a laboratory tissue. The measurement is repeated
3−10 times per sample. The custom measurement is less precise than
an instrumented microindenter, but it is inexpensive, more directly
mimics the adhesion and healing of a bitumen-aggregate interface, and
allows for a wider variety of possible experiments.
16920
■ RESULTS AND DISCUSSION
Chemical Characterization of Surface Oxidation of
Modified Bitumen. Figure 1 shows the FTIR spectra of
rubber-modified bitumen mixed with elemental sulfur. Figure 2
shows the chemical structures of a select variety of stable
oxidized sulfur groups. Even without UV exposure, all samples
cast at 120 °C (90 min) showed some oxidation of the surface
compared to the bulk as seen by the appearance of the
carbonyls (1700 cm−1) and increased sulfoxide (compound 1,
1023 cm−1). Moreover, the sulfur-modified bitumen showed
additional peaks at 3231 cm−1 (OH stretch), 1105 cm−1, and a
doublet at 617/577 cm−1 (Figure 1b, yellow arrows). The peak
at 1105 cm−1 could be due to the SO stretching vibration of
thiosulfoxide (2), sulfinic acid (3b), or sulfinic anhydride
(3c).45 Waste vulcanized rubber is prone to oxidize to yield 2,
especially in the absence of antiaging agents.
The peaks near 600 cm−1 first appear in the surface spectra
of heat-treated sulfur-modified samples, and they become
prominent at the surface of all samples after 100 h UV
exposure. After 200 h UV, the doublet moves closer together
(from 617/577 cm−1 to 595/580 cm−1) suggesting a change in
chemical identity with aging. Sulfonates (6) and sulfates (7)
exhibit bands due to deformation vibrations in the range of the
617/577 cm−1 doublet,45 but the absence of characteristic SO2
stretching bands at 1420−1330 cm−1 and 1200−1145 cm−1 in
https://doi.org/10.1021/acssuschemeng.1c04798
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the heat-only sample suggests that the observed doublet arises
from a different source. One possible source of the doublet is
skeletal deformation vibrations of alkenes that may be a result
of C−S bond scission, particularly if the sulfur atom is oxidized
as in 1 or 2. Figure 3 gives an example of a reaction in which
Figure 3. An example of thermal syn elimination (Ei mechanism) of
sulfoxide to yield sulfenic acid (8) and alkene. Sulfenic acid is reactive
and can condense to yield 2 or oxidize into 3−7.
the sulfoxide C−S bond is cleaved to yield an alkene and
sulfenic acid (8). This reaction only requires heat and proceeds
via the Ei mechanism (thermal elimination).46 8 is unstable,
and high concentrations of 8 will condense to yield 2 within
minutes (Figure 3). In the case of rubber-modified bitumen, it
is thought to be more likely that 8 quickly reacts with other
bitumen molecules or oxidizes into compounds like 3−7.
UV irradiation of the bitumen samples resulted in extensive
oxidation of carbon and sulfur groups. Table 2 lists the
absorption bands that appeared at the bitumen surface after
heat treatment or UV exposure and gives tentative band
assignments. IR absorption spectra of the surface of rubber-
modified bitumen after 100 h UV exposure show a dramatic
decrease in all hydrocarbon bands, most notably, the CH2,3
stretching band (2960−2830 cm−1), CH2,3 deformation band
(1455 and 1376 cm−1), and CH deformation bands (900−700
cm−1, mostly alkenes/phenyls). The large, broad band at
1800−1660 cm−1 results from a high concentration of various
carbonyl and carboxylate groups. The concentration of
oxidized sulfur groups also increases, dominated in particular
by 6 and 7. These compounds are characterized by strong O
SO antisymmetric and symmetric stretching bands around
1420 and 1180 cm−1, respectively. The broad band at 1180
cm−1 could also encompass SO stretching vibrations of 3 or
4. The doublet near 600 cm−1 becomes stronger and less
separated after 200 h UV exposure, suggesting that it no longer
relates to alkenes but to SO2 deformation vibrations of 6 and
7.45
Figure 4 compares the IR spectra of the surface of UV-aged,
sulfur-modified, rubber-modified bitumen (same data as in

Table 2. Prospective Assignments of IR Absorption Bands

in Sulfur-Modified, Rubber-Modified Bitumen Resulting
from Heat Treatment or UV Exposure45

band (cm−1) treatment structure possible vibration

3300−2500 heat/100 h/ R−OH O−H stretch Figure 4. ATR-FTIR spectra of bitumen samples after 200 h UV
200 h UV exposure, comparing rubber-modified bitumen with/without sulfur
alkenes, C−H stretch (typically (same data as Figure 1) to data from ref 38 on nonmodified bitumen.
phenyls ∼3050 cm−1)
Yellow arrow highlights a broad absorption band attributable to OH
1800−1660 heat/100 h/ carbonyls CO stretch
200 h UV stretching of 3b, 6b, or 7b.
1422 −/100 h/200 h 6a, 7a OSO antisymmetric
UV stretch
1270−1090 −/100 h/200 h 6a, 7a OSO symmetric
UV stretch Figure 1) to previously reported spectra of UV-aged bitumen
6c, 7c SO2, SO3 antisymmetric without either rubber or sulfur additives.38 Even though the
stretch previous study used nonmodified bitumen, a different sample
4 SO stretch (1220−1170 preparation (600 nm spin-coated thin film), a weaker UV lamp
cm−1) (UVA-340, Q-Labs), and a different FTIR instrument, the
3a SO stretch (1140−1125 general shape of the spectra are surprisingly similar barring a
cm−1)
1105−1091 heat/100 h/− 2, 3b, 3c SO stretch
few small differences. This similarity demonstrates that after
1050−1000 heat/100 h/ 1 SO stretch (1023 cm−1)
extreme oxidation of bitumen, the remaining nonvolatile
200 h UV residues (mostly sulfate and carbonate minerals) are likely to
6c, 7c SO2, SO3 symmetric stretch, be similar regardless of the initial composition of the bitumen.
SO4 stretch As an analogy, two pieces of wood might come from different
3d SO2 antisymmetric and tree species, but the ash left after burning them could share
symmetric stretch
some of the same chemical compounds. These results suggest
866 −/−/200 h UV 7a S−O−C antisymmetric
stretch that any bitumen mixture is liable to develop a sulfate mineral
3a, 3b S−O stretch layer on its sunlit surface, although this mineral layer will likely
617−577 heat/100 h/ 6a, 7a OSO scissor develop more quickly or more thickly on bitumen with a
200 h UV deformation higher sulfur content, whether that sulfur comes naturally from
7c SO3 bending the crude oil source or is added. Elucidating the effects of this
alkenes skeletal deformation oxide layer on the material performance or environmental
vibration impact will be an important focus of future studies.
16921 https://doi.org/10.1021/acssuschemeng.1c04798
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A very broad band due to OH stretching of acid groups DSR measurement temperature and UV exposure time. HI
(3000−2300 cm−1; 3b, 6b, or 7b) is weakly apparent in the IR increases with temperature as expected and decreases slightly
data (Figure 4). However, many acid groups are probably with 100 h UV aging, although it does not decrease
hydrated, which would shift their SO and S−O absorption significantly more with longer exposure time. In all cases, the
peaks to ranges similar to those of ionic groups (3d, 6c, or 7c). sulfur-modified bitumen shows higher HI values than the
Carboxylic acid compounds have previously been implicated in control.
reducing the moisture-stripping resistance of bitumen in However, all of these metrics apply to bulk bitumen and do
asphalt pavement.47−49 Sulfoxides were found to be less not accurately capture effects that occur at surfaces or
susceptible to water displacement from aggregate surfaces than interfaces. FTIR spectra of subsurface material indicate that
carboxylic acids but more susceptible than nitrogen com- the chemical effects of UV irradiation did not penetrate much
pounds.50 Sulfuric and sulfonic acids are more easily ionizable deeper than ∼0.5 mm for these exposure conditions. DSR
than carboxylic acids and merit further observation in case they measurements of the UV-irradiated samples thus measure
have a similarly damaging effect. some amount of nonirradiated material and cannot be
Compared to the UV-aged control, the surface of the UV- quantitatively compared to the results of other studies unless
aged sulfur-modified sample shows a higher concentration of sample thickness is accurately and precisely controlled.
oxidized sulfur groups. In addition, the phenyl CH Similarly, HI might not be able to fully capture the ability of
deformation band (900−700 cm−1) in the spectra of the bitumen to heal open cracks, especially if the exposed bitumen
sulfur-modified samples appears to be slightly more persistent surfaces of the cracks are oxidized or otherwise chemically
with UV aging compared to the control. This may indicate that distinct from the bulk. Previous work has suggested that even
elemental sulfur could delay degradation of some aromatic in the absence of significant surface oxidation, accumulation
hydrocarbons by oxidizing first. This analysis is preliminary and crystallization of saturate wax at the bitumen surface could
and is complicated by convolution of the CH deformation negatively impact self-healing ability.53
band with S−O stretching vibrations of oxidized sulfur groups, Figure 6 plots the adhesive pull-off force of a soda-lime glass
but it may be of interest for further study. hemisphere (1 cm in diameter) from the surface of rubber-
One mystery is the absence of sulfones (5) in the IR spectra. modified and sulfur-modified bitumen samples as measured by
5 is a stable compound commonly produced from the a custom apparatus. Compared to the control sample before
oxidation of 1 and would show a characteristic absorption any UV exposure, the sulfur-modified bitumen showed greater
band around 1350−1270 cm−1 due to the antisymmetric SO2 adhesion, consistent with DSR measurements and HI values.
stretching vibration. None of the IR spectra of the rubber- After 100 h UV irradiation, the bitumen surfaces were far less
modified or sulfur-modified bitumen show a strong absorption adhesive; the pull-off force of the control sample decreased by
band in that region. That band is shifted up in frequency if 5 is a factor greater than 4, whereas the pull-off force for the sulfur-
halogenated, but elemental analysis in previous work38 did not modified sample saw a 50-fold reduction. The reduction in
show evidence of chlorine or other halogens. A more likely adhesion is illustrative of the effects of surface oxidation and
possibility is that although 5 is generally resistant to thermal UV aging, especially on the sulfur-modified sample. This effect
degradation, it can be susceptible to UV degradation, a is not reflected in the HI values of the sulfur-modified sample,
property that has been studied for the purpose of developing which decreased only modestly with aging and never dipped
photoresist materials.51,52 Degradation of 5 could result in below the values of the control sample. Optical microscope
conversion to 3, 6, or sulfur dioxide gas. images of both samples (Figure 6b,c) show embrittlement and
Viscoelasticity, Healing Index, and Surface Adhesion cracking of the top surface. The aged surface of the sulfur-
of Modified Bitumen. Table 3 lists the dynamic rheological modified sample showed a web of long, straight cracks and no
flexibility, suggestive of a thick, hard, oxidized surface layer.
Table 3. Rheological Properties of Control Bitumen and These physical observations are consistent with the FTIR data
Sulfur-Modified Bitumen at 25 °C showing the surface of the sulfur-modified samples containing
sulfur-
higher concentrations of sulfates, which are brittle mineral
control ±s.d. modified ±s.d. salts. In contrast, the aged control surface showed some
complex shear modulus |G*| 796 0.7 625 2.8 microscale curvature and a few areas where the cracks
(kPa) appeared to open up and reveal fresh bitumen underneath.
phase angle δ 66.06° 0.014 66.83° 0.02 These adhesion measurements show that bulk measures of
NR creep compliance Jnr 3.2 0.2 4.5 0.3 self-healing may not accurately capture the ability (or lack
(Pa−1) @ 0.1 kPa thereof) of asphalt concrete to heal open cracks, especially if
@ 3.2 kPa 3.5 0.07 4.7 0.3 the free bitumen surface is easily oxidized as might be the case
recovery (%) @ 0.1 kPa R 53.3 1.3 50.6 0.4 for high-sulfur bitumen. Certainly, HI is not the only available
@ 3.2 kPa 50.2 0.5 47.9 0.11 metric for healing, as there are a number of competing
healing index (%) HI 23.4 3.0 35.3 2.2 empirical measures, 54,55 but the results highlight the
importance of including metrics that can account for the
properties of the control and sulfur-modified bitumen mixtures unique chemistry and mechanics of free surfaces and how they
as measured by DSR, MSCR, and healing index tests. By every can impact crack healing.53,56
metric listed, the sulfur-modified bitumen is softer, less elastic, Overall, the results show that added sulfur is prone to
and more prone to creep than the control. Therefore, it is not oxidation in bitumen. However, the exact pathway, degree of
surprising that the healing index HI measured by DSR for the oxidation, and subsequent impact may depend on the physical
sulfur-modified bitumen is also higher, since healing ability is state and degree of mixing of the sulfur. This is analogous to
tied to plasticity and molecular mobility. Figure 5 plots HI for crumb-rubber-modified bitumen, where aging characteristics
control bitumen and sulfur-modified bitumen as functions of depend on how the curing method alters the swelling and
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Figure 5. Healing index HI of control bitumen and sulfur-modified bitumen as a function of (a) measurement temperature or (b) UV aging time.
Error bars are one standard deviation.
Figure 6. (a) Pull-off force of a glass hemisphere from control
bitumen and sulfur-modified bitumen mixtures before and after 100 h
UV exposure. Error bars are 95% confidence intervals from 3−10 pull-
off measurements. Optical microscope images of the surfaces of (b)
control bitumen and (c) sulfur-modified bitumen after 100 h UV
exposure.
dissolution of the crumb rubber.57 Liquefied tire rubber in
bitumen is less susceptible to separation and storage instability
than ground tire rubber or crumb rubber. However, if liquefied
rubber blends so thoroughly as to become indistinguishable
from the bitumen matrix, sulfur oxidation would then occur
throughout the material and could therefore make the mixture
more susceptible to age-related hardening. Additionally, crumb
rubber could act as a physical barrier to slow diffusion or as an
oxygen sink in a manner similar to how carbon black or
biochar58 may act as antiaging agents. Depending on the
specific process, liquefaction of rubber could also remove
antiaging additives like carbon black that would otherwise be
retained in crumb rubber.5,59 Similar considerations may also
apply to elemental sulfur, where sulfur dissolved into the
bitumen is less prone to sedimentation but more prone to
oxidation.
■ CONCLUSIONS
The aim of this study was to examine the durability of sulfur-
modified bitumen with respect to oxidative aging and UV
exposure. FTIR data show that bitumen of any composition is
liable to develop a sulfate-rich oxidized mineral layer on its
sunlit surface due to UV degradation, but sulfur-rich bitumen is
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prone to develop a thick layer more quickly. Strictly speaking,
the data do not say that sulfur-rich bitumen is more susceptible
to oxidative degradation since ATR-FTIR only measures the
surface of a sample in contact with the ATR crystal. This
experiment does not measure total oxygen uptake and cannot
account for the diffusion of oxidized compounds deeper into
the material. However, the data do hint that sulfur cross-linked
hydrocarbons may be susceptible to oxidative degradation and
pose a risk to the durability of bitumen. Therefore, it may be
important to retain the antiaging agents in any waste tire
rubber used to modify bitumen. Fully liquefied rubber may be
more prone to degradation than crumb rubber. A partially
liquefied form may be needed to balance the benefits of storage
stability versus chemical stability.
The addition of 3% sulfur plasticized the bitumen mixture as
measured by reductions in complex shear modulus and an
increase in nonrecoverable creep compliance. The self-healing
ability of the bulk material also appeared to be higher for
sulfur-modified bitumen, according to a metric based on shear
modulus. UV aging marginally reduced the healing index of the
bitumen mixtures, but the index is based on a bulk
measurement that cannot fully account for changes that
occur at a free surface. Preliminary surface adhesion measure-
ments showed stronger adhesion by the sulfur-modified
bitumen before UV aging but a dramatic drop to close to
zero adhesion upon 100 h UV exposure. High-sulfur bitumen
mixtures may be less capable of healing cracks and thus be
susceptible to progressive fracture damage. Additionally, future
research and measurements of bitumen’s self-healing proper-
ties need to find ways to better account for the unique
phenomena that can occur at free surfaces or interfaces and
how they may impact crack-healing ability.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.1c04798.
Additional information including photographs of UV-
aged samples and the custom apparatus to measure pull-
off force (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Elham H. Fini − School of Sustainable Engineering and the
Built Environment, Arizona State University, Tempe, Arizona
https://doi.org/10.1021/acssuschemeng.1c04798
ACS Sustainable Chem. Eng. 2021, 9, 16918−16925
ACS Sustainable Chemistry & Engineering
85287-3005, United States; orcid.org/0000-0002-3658-
0006; Phone: 480-965-4273; Email: efini@asu.edu
Authors
Albert Hung − School of Sustainable Engineering and the Built
Environment, Arizona State University, Tempe, Arizona
85287-3005, United States
Mingxia Li − School of Sustainable Engineering and the Built
Environment, Arizona State University, Tempe, Arizona
85287-3005, United States; School of Civil Engineering,
Chongqing Jiaotong University, Chongqing, China 400074
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c04798
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
(Award Numbers 1935723 and 1928795).
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