Construction and Building Materials 227 (2019) 116624

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Effect of organic reagents on high temperature rheological

characteristics of organic rectorite modified asphalt
Meng Jia, Aimin Sha ⇑, Zengping Zhang, Jiange Li, Dongdong Yuan, Wei Jiang
Key Laboratory for Special Area Highway Engineering of Ministry of Education, Chang’an University, Xi’an, Shaanxi 710064, PR China

h i g h l i g h t s

Organic reagents affect the rheological behavior of OREC modified binder.

Organic reagent containing benzyl groups are preferred from high temperature property.

The traffic loading grade of OREC modified binders is determined.

a r t i c l e i n f o a b s t r a c t

Article history: The molecular structure of organic reagents has a great effect on properties of organic rectorite (OREC)
Received 8 April 2019 modified asphalt binder. This paper aims at comparing the influence of molecular chain length and ben-
Received in revised form 24 July 2019 zyl group on the high temperature rheological characteristics of OREC modified binder. Here, three
Accepted 1 August 2019
organic quaternary ammonium salts, including dodecyl trimethyl ammonium chloride (DTAC), dodecyl
Available online 12 August 2019
dimethyl benzyl ammonium chloride (DBAC) and octadecyl trimethyl ammonium chloride (OTAC), were
selected as REC modifiers to prepare ORECs. These ORECs were then employed to modify base binder,
Keywords:
respectively. The X-ray diffraction (XRD) test and thermogravimetric (TG) test were conducted to study
Asphalt binder
Rectorite
the structure characteristics and thermal behavior of ORECs and corresponding modified binders. The
Organic reagent high temperature rheological behavior, rutting and stress susceptibilities of OREC modified binders were
Organic treatment evaluated by the temperature and frequency sweep tests, multiple stress creep recovery (MSCR) test.
Susceptibility Results indicate that, the organic reagent affects the rheological behavior of OREC modified binder not
Rheological behavior only by enlarging the basal spacing of REC (specific surface area), but also directly by specific functional
groups (e.g. benzyl group). Moreover, the organic reagent with longer molecular chains (18 carbon
atoms) or containing benzyl groups is conductive to the improvement in elastic property and stiffness,
and reduction in rutting and stress susceptibilities of OREC modified binder. The comparison demon-
strates that DBAC containing benzyl groups exhibits better effect. Therefore, organic reagents containing
benzyl groups are preferred to obtain OREC modified binder with excellent high temperature property.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction researches of which in China originated in the late 1970s, later

Asphalt with good viscoelastic behaviors, has been widely uti-
lized as binder in high-grade road pavement [1–3]. However, in
general, base asphalt binder is easy to soften at high temperature
and be brittle at low temperature [4]. Also, traffic and vehicle load
have rapidly increased in decades. With these in mind, effective
methods should be applied to obtain the asphalt binder meeting
requirement for the pavement use. And among them, the modifica-
tion technology has been actively studied. Polymer modified
asphalts (PMA) are the most commonly used technology, relevant
⇑ Corresponding author.
E-mail address: ams@chd.edu.cn (A. Sha).
than those aboard [5,6]. Research results have revealed that, a
small amount of polymers (e.g. SBS, SBR) can significantly improve
technical properties of binder [7,8]. However, polymers generally
distribute in asphalt matrix without obvious chemical reaction,
finally forming unstable system [9]. Polymers in asphalt matrix
tend to segregate and degrade during production, thermal storage
and paving of PMA [10]. As a consequence, chemical modification
technology is required to be sought.
Recently, layered silicates at nanoscale, primarily consist of
montmorillonite (MMT), rectorite (REC), vermiculite (VMT), have
been extensively utilized to modify base asphalt binder [11–13].
It was found that asphalt molecules were able to intercalate into
interlayers of layered silicates to form stable system [4,14,15].

https://doi.org/10.1016/j.conbuildmat.2019.08.005
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 M. Jia et al. / Construction and Building Materials 227 (2019) 116624
On the whole, the source and preparation method have an extre-
mely important impact on the structure (e.g. interlayer space,
aspect ratio) and property (e.g. cation exchange capacity) of these
layered silicates [16], and wherein MMT has got the most attention
in asphalt modification, as MMT can endow asphalt binder with
excellent properties (e.g. mechanical property, thermal storage sta-
bility and aging resistance) [17,18]. REC has the similar layered
structure with MMT, which is a 1:1 regularly interstratified clay
mineral with alternate pairs of dioctahedral mica and dioctahedral
smectite [19]. In comparison with MMT, REC, with the larger
aspect ratio, restricts the movement of asphalt molecules more
dramatically. Hence, REC, as the asphalt modifier, is expected to
have a better application prospect than MMT.
There exists a certain amount of exchangeable cations (e.g. Na+,
Ca , Al3+) in REC galleries, and these cations can be exchanged
2+
with reagent molecules through organic treatment (Fig. 1), the pro-
cess of which expands REC basal spacing and subsequently pro-
motes the intercalation of asphalt molecules [4,15,20].
Additionally, hydrophilic REC is converted to organophilic one,
improving the compatibility with asphalt binder [21]. Relevant
works have also been carried out in nearly ten years, which is sum-
marized in Table 1.
According to the literature review, researchers have provided a
series of valuable information on the use of REC and OREC for
asphalt modification, chiefly including the following points: first,
asphalt molecules were able to intercalate into REC and OREC gal-
Fig. 1. Schematic of organic treatment to REC.
Table 1
Literature review on OREC modified binders.
Year Authors Organic reagent type
2007 Yu et al. [22] – Semi-
2007 Chen et al. [23] – Exfoliated
2013 Zhang et al. [24] Octadecyl dimethyl benzyl ammonium
chloride (ODBA)
2014 Du et al. [11] Cetyltrimethyl ammonium bromide (CTAB)
2014 Zhang et al. [25] Octadecyl dimethyl benzyl ammonium
chloride (ODBA)
2014 Zhang et al. [15] Octadecyl dimethyl benzyl ammonium
chloride (ODBA)
2015 Zhang et al. [21] Cetyltrimethyl ammonium bromide (CTAB)
and octadecyl dimethyl benzyl ammonium
chloride (ODBA)
leries, leading to the excellent storage stability of REC and OREC
modified binders; second, REC and OREC particles obstructed the
movement of asphalt molecules and oxygen infiltration, thus
improving the good high temperature stability and aging resis-
tance of asphalt binder; moreover, organic treatments to REC usu-
ally improved asphalt properties more effectively as compared to
pristine REC, and properties of modified binders was mainly
dependent on the layered structure of REC and OREC.
We noticed that, most literatures reported the effect of OREC on
asphalt properties primarily from the type of OREC structure
(intercalated structure, semi-exfoliated structure and full-
exfoliated structure). Specifically, most researchers used one kind
of organic reagent as REC modifier to prepare the OREC with large
specific surface area. In most cases, OREC with full-exfoliated
structure has the largest specific surface area, followed by that
with semi-exfoliated structure, intercalated structure.
However, little research results have been reported at this point
concerning the preparation of OREC from the selection of organic
reagents with different molecular characteristics. In fact, the
molecular structure of organic reagents has a key impact on the
layered structure of OREC, and may directly affect asphalt proper-
ties. For this reason, Zhang et al. [21] revealed that the steric hin-
drance effect of the benzyl group in organic reagent hindered the
insertion of reagent molecules into REC layers. Remarkably, there
are many kinds of organic reagents with different molecular struc-
tures. Almost no studies have been performed to qualitatively
Layered General conclusion
structure
OREC sheets could restrict the movement of asphalt molecules, leading to
exfoliated the good high temperature stability.
OREC with exfoliated structure hindered the movement of asphalt
molecules more effectively, hence increasing viscosity, fracture failure
energy and aging resistance of asphalt binder.
Intercalated The OREC layers restrained the oxygen penetration, thus improving aging
resistance of binder.
Semi- OREC particles hindered the oxygen penetration and increased its average
exfoliated path length during situ thermal aging, so thermal aging resistance of
asphalt binder was improved.
Intercalated The thermal aging resistance of the binder was improved with the
introduction of REC, further enhanced by its organic modification.
Semi- The influence of OREC on physical properties of SBS modified asphalt
exfoliated before and after aging depended on its nature; OREC possessed excellent
compatibility with SBS modified binder.
CTAB-REC: The steric hindrance effect of the benzyl group in ODBA, which hinders the
Exfoliated insertion of ODBA into REC layers; the CTAB-OREC with exfoliated
ODBA-REC: nanostructure prevented the oxygen infiltration more efficiently,
Intercalated
 M. Jia et al. / Construction and Building Materials 227 (2019) 116624 3

compare the influence of different molecular characteristics on ð1:2  am1 M Þ

properties of OREC modified binder.
Our research team has reported physical properties and
microstructures of OREC modified binders [4]. We found that,
organic reagents noticeably influenced the physical properties
and microstructure of OREC modified binder. In reality, asphalt
binder is a typical viscoelastic material, and in the majority of
cases, asphalt pavement distresses at high temperature are attrib-
uted to the change of asphalt rheological behaviors which have not
been discussed in that work [4]. So, in this study, we evaluated the
effect of organic reagents on the high temperature rheological
characteristics of OREC modified binder, and then relationships
between the molecular structure of organic reagents and high tem-
perature performance grade, as well as traffic loading grade of
OREC modified binder were built. Besides, rutting and stress sus-
ceptibilities of modified binders were also discussed.
2. Experimental
2.1. Materials
2.1.1. Base asphalt binder
The base asphalt binder with 80/100 pen grade was produced in SK Co., Korea,
and its properties are listed in Table 2.
2.1.2. REC
The rectorite (REC) was bought from Shunhehuatao Co., Hubei, China, and its
essential information is displayed in Table 3.
2.1.3. Organic reagent
The organic reagents included dodecyl trimethyl ammonium chloride, dodecyl
dimethyl benzyl ammonium chloride and octadecyl trimethyl ammonium chloride,
designated as DTAC, DBAC and OTAC, respectively. These reagents, with purity of
95%, were bought from Sinopharm Chemical reagent Co., Ltd, China. Regarding
the molecular structure, DBAC has one more benzyl group in one main chain than
DTAC, whereas OTAC has six more carbon atoms in one main chain than DTAC.
2.2. Preparation of ORECs and modified binders
The preparation procedures of ORECs were as follows [4]: REC was blended with
deionized water in the weight ratio of 1: 30, at the stirring speed of 300r/min and
stirring time of 2 h. A certain amount of organic reagent, gained by Eq. (1), was
slowly added after the solution was heated to 80 °C. Following that, this suspension
was stirred for 2 h. The precipitate was then washed with deionized water in many
times until no residual organic reagent existed in water. The precipitate was subse-
quently placed in oven at 105 °C for 6 h to obtain the dried precipitate. Finally, the
dried precipitate was ground and sieved to obtain the OREC with the particle size no
>300 mesh.
m¼ ð1Þ
100  1000
in which, m represents the mass of organic reagent; a is the REC cation exchange
capacity (43 mmol/100 g); m1 is the REC mass; M represents the relative molecular
mass of organic reagent.
Modified asphalt binders were prepared by the traditional melt-mixing method.
Details were as the following procedures: base binder was firstly heated to
140 ± 10 °C to become fluid. The 3 wt% modifier by asphalt weight was slowly
added into binder at 2000r/min. This composite was subsequently stirred at
3000r/min for 60 min to gain the modified binder.
The specific procedures are shown in Fig. 2.
2.3. Experimental methods
2.3.1. X-ray diffraction test
To obtain the layered structure information of REC and ORECs, a diffractometer
(Cu-Ka radiation, 40 kV, 50 mA) was followed to measure the diffraction angle of
REC and ORECs at room temperature. The scan at the speed of 0.02°, ranged from
3° to 10° for REC and ORECs, as well as from 0.6°to 10° for modified binders. Con-
sidering that the small modifier content (3 wt%) may be not enough for the diffrac-
tion peak to be seen, REC and ORECs were separated from modified binders in terms
of the relevant reports by Zhang et al. [15,26], and then measured by diffractometer.
The basal spacing (d001), calculated via the Bragg equation in Eq. (2), was uti-
lized to describe the layered structure information.
2d001 sinh ¼ nk ð2Þ
in which, h is the diffraction angle (°); k is the wavelength (0.15406 nm); n is the
diffraction order.
2.3.2. Thermogravimetric test
Since organic reagent molecules in ORECs directly affect properties of OREC
modified binders, the thermal stability of these ORECs should be considered. To this
end, the thermos gravimetric (TG) test was performed on REC and ORECs in a nitro-
gen atmosphere, and from the room temperature to 600 °C at the heating rate of
10 °C/min.
2.3.3. Temperature sweep test
The temperature sweep tests were carried out by dynamic shear rheometer
(DSR) in accordance with ASTM D7175SPS:xlink.href::astm:D7175||xlink.type::sim
ple. Temperature sweeps ranged from 60 °C to 80 °C with an increment of 5 °C and a
fixed frequency of 10 rad/s.
Based on the result of temperature sweep tests, three parameters including
storage modulus (G0 ), phase angle (d), complex modulus (G*) can characterize the
viscoelastic behavior of OREC modified binders at high temperatures. In detail,
the larger elastic property reflects the larger recoverable deformation of asphalt
binder after removal of load, as well as more stored energies under loading cycles,
which can be evaluated by the G0 [27–29]; the d is defined as the lag between the
applied shear stress and resulting shear strain, and it presents the ratio between
elastic and viscous components of asphalt binder [30,31]; G* is defined as the ratio
of maximum stress to maximum strain, indicating the stiffness of binder [32–34].

Table 2
Properties of base asphalt binder.

Test items Unit Result Specifications

Penetration (25 °C,100 g,5s) 0.1 mm 89.4 80–100
Softening point °C 45.6 42–52
Ductility (5 cm/min, 15 °C) cm 121 100
Viscosity at 60 °C Pas 283 160
Viscosity at 135 °C Pas 0.342 –
Density g/cm3 1.0003 –
Solubility % 99.7 99.5
RTFOT (163 °C, 85 min) Penetration ratio % 63.0 57
Ductility cm 28 8
Softening point °C 52.8 –

Table 3
The essential information of REC.

Specific area (g/cm3) Cation exchange capacity (mmol/100 g) Chemical composition (%, w/w)
Na2O MgO Al2O3 SiO2 K2O CaO Fe2O3
73 43 2.76 0.385 37.4 52.6 1.46 1.64 0.241
4 M. Jia et al. / Construction and Building Materials 227 (2019) 116624

Fig. 2. The preparation procedures of ORECs and modified binders.

Additionally, the rutting resistance factor (G*/sind) is able to depict the rutting
susceptibility of binder [35,36]. To determine the high temperature performance
7
grade of OREC modified binders, failure temperatures of them were firstly deter- 30 C 40 C 50 C 60 C 70 C T/°C a(T)
mined based on G*/sind results for non-aged and RTFO state binders [35]. The fitting curve by Sigmodal Model
6 30 1.986
40 1.428
50 0.637
2.3.4. Frequency sweep test 5
lg(G*)/Pa

60 0
The frequency sweep tests were also performed by the DSR machine according 70 -0.542
to ASTM D7175SPS:xlink.href::astm:D7175||xlink.type::simple. Frequency sweeps 4 Parameters Results
ranged from 0.1 to 10 rad/s at various temperatures (30 °C, 40 °C, 50 °C, 60 °C and
70 °C) with the control strain of 10%. The gap and diameter were 2 mm and
δ 1.768
8 mm at 30 °C, while the gap and diameter were 1 mm and 25 mm at other test
3 α 3.37
temperatures. β 0.689
As known, the viscoelastic behavior of binder is characterized by the 2 γ -1.143
temperature-dependence and time-dependence [27]. The viscoelastic behavior at R-Square 0.993
high temperature and short loading time can be shifted to that at low temperature 1
and long loading time in terms of the time-temperature superposition principle
-2 -1 0 1 2 3
(TTSP) [30,37]. This corresponding shift at a given temperature is generally deter-
mined by the shift factor, as seen in Eq. (3), which makes it possible to shift jG*jor lg(
jG*/sindjvalues from other test temperatures and frequencies to a reference temper-
r)/rad/s
ature. Any temperature among test temperatures can be selected as the reference
Fig. 3. The generation of mater curve for base binder.
temperature [34], where this work selected 60 °C as the reference temperature.
The G* and G*/sind master curves were generated by the Sigmodal Model (as seen
in Eq. (4)) and nonlinear least squares fitting with the help of Matlab software
[30,34].
2.3.5. Multiple stress creep recovery test
logðxr Þ ¼ logðxÞ þ logðaðT ÞÞ ð3Þ The DSR machine was also employed to implement the multiple stress creep
recovery (MSCR) test for RTFO state binders in accordance to ASTM D7405SPS:xli
nk.href::astm:D7405||xlink.type::simple. The test temperatures included 52 °C,
a 58 °C, 64 °C and 70 °C. These tests comprised 1 s creep under load and subsequent
logjY j ¼ d þ ð4Þ
1 þ ebþclogðxr Þ 9 s creep recovery after the removal of load. The 0.1 kPa stress level was applied at
10 cycles, followed by 3.2 kPa also at 10 cycles.
in which, xr is the reduced frequency at the reference temperature (rad/s); x is the The R(e), Jnr(e) and Jnr-diff, calculated by Eq. (5), Eq. (6) and Eq. (7), are able to
frequency at test temperature (rad/s); a(T) is the shift factor; jYj is the complex mod- assess the recovery ability, rutting resistance and stress susceptibility of binders,
ulus or rutting resistance factor (Pa); d, a, b and c are coefficients. respectively [38,39]. Also, the traffic loading grades of binders can be determined.
As for the fitting procedure of master curve, an example of base binder used in Fig. 4 presents one cycle of creep and recovery stages. In the recovery stage, there
this research is illustrated in Fig. 3. The shift factor is 0 at the 60 °C reference tem- exists non-recoverable strain for binder.
perature. The G* data at other temperatures are horizontally shifted according to  n 
the shift factors obtained by nonlinear least squares fitting mentioned above. Con- 1 X 10
cc  cnr  100
RðeÞ ¼ ð5Þ
struction of G* and G*/sind master curves for other binders is the same as that for 10 n¼1 cnc  cn0
base binder.
 M. Jia et al. / Construction and Building Materials 227 (2019) 116624 5

Creep stage Recovery stage value than REC, suggesting that the organic treatment expands
REC galleries. Among these ORECs, OTAC-OREC possesses the lar-
1 cycle gest d001 value following by DBAC-OREC, DTAC-OREC, which is
c related to the molecular structure of organic reagents; that is,
Strain (%)

OTAC, having the longest molecular chains, is more conductive to

r expanding REC galleries than DBAC which has benzyl groups. It
can also be found that, in Table 4, REC and ORECs show the signif-
icantly larger d001 value after incorporated into base binder. This
Non-Recoverable Strain denotes that asphalt molecules seemingly intercalate into their
galleries, which has been reported by previous research [4]. In
addition, only OTAC-OREC modified binder exhibits no d001-
reflection peak in the range of 0.6–10°, demonstrating the forma-
0 2 4 6 8 10 tion of exfoliated structure [21,40]. By contrast, other kinds of
T(s) modified binders are all intercalated nanostructures. Therefore,
OTAC-OREC particles have the largest specific surface area in
Fig. 4. One cycle of creep and recovery procedures. asphalt matrix.

1 X 10
cnr  cn0 3.2. Thermal behavior analysis
Jnr ðeÞ ¼ ð6Þ
10 n¼1 e
Fig. 6 presents the TG test results for REC and ORECs. It is
½J ð3:2Þ  Jnr ð0:1Þ  100 observed that, the mass losses all start at the initial temperature,
Jnrdiff ¼ nr ð7Þ chiefly caused by the volatilization of free water in their surfaces
J nr ð0:1Þ
[30]. This part of mass loss has little effect on the thermal stability
where, cn0 and cnc are the initial and final creep strains in the creep stage; cnr is the of ORECs. After that, the sharp mass loss of ORECs is caused by the
finial strain in the recovery stage. e is the applied stress (0.1 kPa or 3.2 kPa) in this
decomposition of organic cations (i.e. organic reagents) in galleries
test.
[41]. OTAC-OREC has the lowest initial decomposition tempera-
ture, as 150.7 °C, whereas DTAC-OREC possesses almost the same
3. Results and discussion decomposition temperature (201.3 °C) as DBAC-OREC. As a result,
the preparation temperature of modified binders (140 ± 10 °C) pre-
3.1. Structure analysis vents organic cations from decomposing. Furthermore, combined
with the XRD test result, it can be found that, ORECs with the larger
Fig. 5 presents the XRD patterns, from which the diffraction d001 value have the worse thermal stability with respect to REC,
angles (2h) and corresponding basal spacings (d001) are extracted which can be explained that the expansion between OREC sheets
and organized in Table 4. Basically, the d001-reflection peak deter- reduces the binding effect on organic cations.
mines the layered structure of layered silicates [21,40]. In detail, no
appearance of d001-reflection peak in the range of 0.6°–10° means
3.3. Analysis of temperature sweep test results
the exfoliated structure, while the existence of peak indicates the
intercalated structure. From Table 4, ORECs have the larger d001
3.3.1. Storage modulus, complex modulus and phase angle
Fig. 7 provides the storage modulus (G0 ), complex modulus (G*)
and phase angle (d) results for binders. With temperature rising,
REC REC modified binder
DTAC-OREC DTAC-OREC modified binder
DBAC-OREC DBAC-OREC modified binder
OTAC-OREC OTAC-OREC modified binder 100
Intensity

95
201.3 C
Mass (%)

90 150.7 C

85 REC
DTAC-OREC
80 DBAC-OREC
OTAC-OREC
75
1 2 3 4 5 6 7 8 9 10 0 100 200 300 400 500 600
2 ( ) Temperature (°C)

Fig. 5. The XRD patterns for modifiers and corresponding modified binders [4]. Fig. 6. The TG test results for modifiers.

Table 4
The diffraction angles and corresponding basal spacings.

REC DTAC-OREC DBAC-OREC OTAC-OREC

Origin In binder Origin In binder Origin In binder Origin In binder
2h (°) 3.98 2.84 3.24 2.10 3.06 1.77 3 
d (nm) 2.22 3.11 2.72 4.20 2.88 4.99 2.94 >5.19
6 M. Jia et al. / Construction and Building Materials 227 (2019) 116624

3.0
Base
REC
DTAC-OREC
2.5 DBAC-OREC
OTAC-OREC

2.0

lgG (Pa)
1.5

1.0

(a)
0.5
60 65 70 75 80
T( C )

4.0 90

88
3.5
lgG*(Pa)

() 86
3.0
84

2.5
82

(b) (c)
2.0 80
60 65 70 75 80 60 65 70 75 80
T( C ) T( C )

Fig. 7. The temperature sweep test results for binders at various temperatures: (a) Storage modulus; (b) Complex modulus; (c) Phase angle.

the G0 and G* values decrease while the d values increase, irrespec- which makes the restriction of DBAC-OREC on asphalt molecules
tive of the modifier type. This manifests that the increased temper- more significantly than that of OTAC-OREC with exfoliated nanos-
ature weakens the elastic property but enhance the viscous tructure. This provides a new idea for researchers — more attention
property. Compared with base binder, modified binders, with the should be paid to the selection of organic reagent than only to the
larger G0 and G* values, have the greater stiffness and elastic prop- OREC structure.
erty, which is primarily due to two reasons: first, modifiers in
asphalt matrix occupy part of the free volume between asphalt
molecules, which strengthens the restriction on movement of 3.3.2. Rutting resistance factor
asphalt molecules; second, a certain amount of asphalt molecules The rutting resistance factor (G*/sind) evaluates the rutting sus-
intercalates into galleries, which increases the difficulty in the ceptibility of these binders (Fig. 8). As a rule, the large G*/sind value
movement of asphalt molecules as well [4,42].
With regard to the influence of modifier type, DBAC-OREC, hav-
ing the greatest G0 and G* values, endows base binder with the lar- 4.0
Unaging Base RTFO aging
gest stiffness and elastic property, followed by OTAC-OREC, DTAC- REC
OREC, and REC ranks the lowest. It seems that organic treatments DTAC-OREC
DBAC-OREC
to REC help to the improvement in stiffness and elastic property. 3.5 OTAC-OREC
(Pa)

And for organic reagent, the existence of benzyl groups has better
effect than the increase in molecular chain length (from 12 carbon
atoms to 18 carbon atoms). This phenomenon can be interpreted as
lg(G*/sin

3.0
the fact that, organic treatments to REC improve its compatibility G*/sin =2.2kPa
with asphalt matrix and meanwhile, enlarge its basal spacing; as
a result, ORECs have the larger specific surface area to restrict G*/sin =1kPa
the movement of asphalt molecules, leading to the larger storage 2.5
energy and recovery ability [4]. Moreover, it can be inferred from
the XRD result, OTAC-OREC possesses the largest specific surface
area in asphalt matrix, followed by DBAC-OREC, DTAC-OREC, 2.0
which determines that OTAC-OREC and DBAC-OREC are stronger 60 65 70 75 80 60 65 70 75 80
in blocking asphalt molecules when compared with DTAC-OREC. T( C) T( C)
It should be pointed out that, however, rigid benzyl groups
increase the adsorption of DBAC-OREC on asphalt molecules, Fig. 8. The G*/sind results for unaged and RTFO aged binders within 50–80 °C.
 M. Jia et al. / Construction and Building Materials 227 (2019) 116624 7

Table 5
The high temperature PG determinations.

Asphalt type The corresponding temp. (°C) Failure temp. High temperature PG determination
(°C)
G*/sind = 1 kPa G*/sind = 2.2 kPa
Base 65.93 65.63 65.63 PG64
REC 69.93 67.43 67.43 PG64
DTAC-OREC 71.07 67.84 67.84 PG64
DBAC-OREC 73.74 70.29 70.29 PG70
OTAC-OREC 71.89 68.56 68.56 PG64

increases, which is ascribed to the fact that, the low frequency rep-
6.0 resents the loading for a long time so that the viscoelastic behavior
Base
5.5 REC of binders can well reflect under the longer loading time; the
DTAC-OREC
increase in frequency is equivalent to the decline of loading time,
5.0 DBAC-OREC
OTAC-OREC so differences in viscoelastic behavior between these binders are
4.5 increasingly difficult to express.
4.0
3.4.2. Rutting resistance factor
3.5 Fig. 10 presents the G*/sind master curves at 60 °C. As expected,
3.0 for all binders, the G*/sind value goes up as the frequency
increases, indicating that the increase in frequency decreases the
2.5
rutting susceptibility of base binder. When compared with base
2.0 binder, modified binders have the larger G*/sind value, demon-
1.5 strating the smaller rutting susceptibility. With respect to the
-2 -1 0 1 2 3 influence of modifier type, DBAC-OREC reduces the rutting suscep-
tibility most noticeably, and OTAC-OREC, DTAC-OREC and REC fol-
low. In addition, it can also be observed that, in Fig. 10, G*/sind
Fig. 9. The G* master curves at 60 °C for binders. values of base binder are remarkably lower than those of modified
binders under low frequencies, while these differences gradually
decrease with the frequency increasing. As analyzed above, the
reflects the small rutting susceptibility and vice versa. So, it can be increase in frequency is actually equal to the shorter loading time.
obtained that, in Fig. 8, the increased temperature enhances rutting As a consequence, the improvement of modifiers in the viscoelastic
susceptibility of binders. Besides, by the presence of modifiers, the property can better reflect at relatively longer loading time.
rutting susceptibility of base binder is noticeably reduced, irre-
spective of the state (non-aged or RTFO state). The comparison 3.5. Analysis of MSCR test results
between these modifiers shows that, DBAC-OREC decreases the
rutting susceptibility most effectively, followed by OTAC-OREC, 3.5.1. Accumulated strain
DTAC-OREC and REC, which is associated with the improvement Fig. 11 illustrates the accumulated strain results at 3.2 kPa
in asphalt stiffness as discussed for G* results. stress level and 60 °C. From Fig. 11(a), modified binders, with the
smaller total accumulated strain, exhibit the better deformation
3.3.3. Determination of high temperature performance grade resistance as compared to base binder, which probably stems from
In order to build the relationship between the molecular char- the larger elastic property and stiffness of these modified binders.
acteristics of organic reagents and the high temperature perfor- The comparison between these OREC modified binders demon-
mance grade of OREC modified binder, failure temperatures of strates that, DBAC-OREC modified binder has the best deformation
binders are listed in Table 5. Clearly, only DBAC-OREC modified resistance, followed by OTAC-OREC modified binder and DTAC-
binder has the failure temperature higher than 70 °C, whereas fail-
ure temperatures of other binders are in the range of 64–70 °C,
demonstrating that only DBAC-OREC containing benzyl groups 6
Base
has ability to enhance the high temperature performance grade REC
(PG) of base binder. DTAC-OREC
5 DBAC-OREC
lg(G∗/sinδ)/Pa

OTAC-OREC
3.4. Analysis of frequency sweep test results
4
3.4.1. Complex shear modulus
The G* master curves at 60 °C are shown in Fig. 9. The G* value
3
is found to increase with the frequency increasing, regardless of
the modifier type. This can indicate that asphalt binders have
greater stiffness to resist deformation at larger frequency. At any 2
given temperature, DBAC-OREC modified binder possesses the lar-
gest G* value following by OTAC-OREC modified binder, DTAC-
OREC modified binder, REC modified binder and base binder, which 1
further verifies that, REC and ORECs are capable of enhancing the -2 -1 0 1 2 3
stiffness. And wherein, DBAC-OREC endows base binder with the lg(ωr)/rad/s
largest stiffness. Furthermore, it is noteworthy that, the G* differ-
ences between these binders gradually decrease as the frequency Fig. 10. The G*/sind master curves at 60 °C for binders.
8 M. Jia et al. / Construction and Building Materials 227 (2019) 116624

120
Base Base REC DTAC-OREC DBAC-OREC OTAC-OREC
20
Accumulated strain (%)

Accumulated strain (%)

REC σ/E 1.68 1.22 1.17 0.84 1.02
100 DTAC-OREC σ/η 11.22 11.14 10.38 8.11 8.88
DBAC-OREC 16 R-Square 0.99976 0.99975 0.99968 0.9995 0.99965
80 OTAC-OREC

12
60

40 8

20 4

0 0
0 10 20 30 40 50 60 70 80 90 100 0.0 0.2 0.4 0.6 0.8 1.0
T(s) T(s)
(a) (b)
Fig. 11. The accumulated strain results for binders at 3.2 kPa and 60 °C: (a) 0–100 s; (b) 0–1 s.

25 containing benzyl groups, has the best effect. These results can also
Base
be explained by the restriction on asphalt molecules as discussed
R(3.2)/%

20 REC
DTAC-OREC in Section 3.3.1.
15 DBAC-OREC
OTAC-OREC For the purpose of investigating the creep behavior of asphalt
10 binders, the accumulated deformation results within the range of
5 0–1 s are displayed in Fig. 11(b). It can be observed that, the exis-
0 tence of modifiers decreases the creep behavior of base binder.
lg[Jnr(3.2)]/kPa-1

0.8 DBAC-OREC modified binder shows the greatest decrement, fol-

lowed by OTAC-OREC modified binder, DTAC-OREC modified bin-
0.4 der, REC modified binder, which is mainly associated with their
0.0 stiffness. Furthermore, it can also be seen that, the accumulated
strain for all binders increases linearly with time that exhibit char-
-0.4 acteristics of linear viscous fluid, reflecting that the main deforma-
tion is all viscous flow at high temperature, and this characteristics
52 54 56 58 60 62 64 66 68 70 can be well described by the Maxwell model (Eq. (8)). Results are
T/s shown in Fig. 11(b) as well. The correlation coefficients reach to
Fig. 12. The recovery percent and non-recoverable creep compliance results for
0.999, demonstrating that the Maxwell model is suitable to fit
binders at various temperatures. the creep behavior of REC and OREC modified binders.
r r
eðtÞ ¼ þ t ð8Þ
E g

where, r is the initial stress (3.2 kPa); E is the instantaneous elastic

modulus; g is the viscous coefficient.

3.5.2. Recovery percent and non-recoverable creep compliance

The recovery percent (R) and non-recoverable creep compliance
(Jnr) results at 3.2 kPa stress level and various temperatures are
shown in Fig. 12. Generally speaking, the larger R and Jnr values
correspond to the greater recovery ability and worse rutting resis-
tance, respectively. In view of this, it can be obtained that, an
increase in test temperature impairs the recovery ability and rut-
ting resistance, irrespective of the modifier type, which may be
due to the fact that, the increased temperature accelerates the
transition of asphalt binder to viscous fluid. Moreover, the Fig. 12
also indicates that, DBAC-OREC modified binder is best in recovery
ability and rutting resistance following by OTAC-OREC modified
binder, DTAC-OREC modified binder, REC modified binder and base
binder, which can be explained by the improvement in elastic
property and stiffness of base binder.
Fig. 13. Percent differences between Jnr(0.1) and Jnr(3.2) at various temperatures.

3.5.3. Stress susceptibility

The Jnr-diff results at various temperatures are presented in
OREC modified binder, and the REC modified binder ranks the low- Fig. 13. Regardless of the modifier type, the Jnr-diff value is found
est. It is obvious that, organic treatments to REC improve the defor- to rise with temperature going up. Obviously, the increased tem-
mation resistance of base binder more effectively; DBAC-OREC, perature enhances the stress susceptibility. As anticipated, modi-
 M. Jia et al. / Construction and Building Materials 227 (2019) 116624
Table 6
The traffic loading grade of binders.
Asphalt samples Jnr(3.2)/kPa1
52 °C 58 °C
Base 0.62 1.51
REC 0.55 1.35
DTAC-OREC 0.49 1.20
DBAC-OREC 0.36 0.78
OTAC-OREC 0.43 0.93
fied binders exhibit the significantly lower Jnr-diff value when com-
pared with base binder, denoting that the existence of modifiers
results in the decrease of stress susceptibility, which is probably
linked to the improvement of modifiers in asphalt stiffness.
Besides, the existence of ORECs help to the reduction in stress sus-
ceptibility, and among which, DBAC-OREC endows base binder
with the smallest stress susceptibility, and the stress susceptibility
of OTAC-OREC modified binder is smaller than that of DTAC-OREC
modified binder. It appears that, the molecular structure of organic
reagents has an impact on stress susceptibility. Moreover, in terms
of AASHTO MP19, the Jnr-diff value should be <75% [43]. Evidently,
all binders meet the requirement in the range of test temperatures
except base binder at 70 °C.
3.5.4. Determination of traffic loading grade
The traffic loading grade of these binders is determined in
accordance with the AASHTO MP19 [43], the result of which is
shown in Table 6. DBAC-OREC modified binder always exhibits
the highest traffic loading grade, and OTAC-OREC modified binder
and DTAC-OREC modified binder follow, indicating that the incor-
poration of ORECs dramatically enhances the capacity of binder to
withstand traffic loads. However, REC modified binder displays the
same traffic loading grade as base binder at any given temperature.
According to the above discussion, REC is able to increase the elas-
tic property and stiffness of base binder. Thus, the existence of REC
is likely to slightly improve the ability of binder to withstand traffic
loads.
Note: Grade ‘‘S”: Standard traffic (ESALs < 107 times); Grade
‘‘H”: Heavy traffic (ESALs = 107–3  107 times); Grade ‘‘V”: Very
heavy traffic [ESALs > 3  107 times or standing traffic (traffic
velocity < 20 km/h)]; Grade ‘‘E”: Extremely heavy traffic
[ESALs > 3  107 times and standing traffic (traffic veloc-
ity < 20 km/h)] [3,43].
4. Conclusions

For OREC, the larger basal spacing usually leads to the worse
thermal stability, which should be considered when selecting
the preparation temperature of OREC modified binders so as
to prevent the organic cations in OREC galleries from
decomposing.

The organic reagent with longer molecular chains or containing
benzyl groups is conductive to the improvement in elastic prop-
erty and stiffness, and reduction in rutting and stress suscepti-
bilities of OREC modified binder.

DBAC-OREC, having benzyl groups in its galleries, improves
elastic property and stiffness and meanwhile, reduces rutting
and stress susceptibilities more dramatically than OTAC-OREC
with larger specific surface area. As a result, from the perspec-
tive of high temperature property, organic reagents containing
benzyl groups are recommended to prepare OREC suitable for
asphalt matrix.

The organic reagent affects rheological behaviors not only by
enlarging the basal spacing of REC, but also directly by specific
functional groups (e.g. benzyl group), which provides a new
9
Traffic loading grade
64 °C 70 °C 52 °C 58 °C 64 °C 70 °C
3.41 8.05 V H S –
3.02 5.92 V H S –
2.59 4.94 E H S –
1.84 3.21 E V H S
2.03 3.91 E V S S
perspective for researchers — more attention should be paid
to the selection of organic reagent than only to the OREC
structure.
Declaration of Competing Interest
None.
Acknowledgements
This work was supported by the National Key R&D Program of
China (No. 2018YFB1600200) and the National Natural Science
Foundation of China (NSFC) (Grant No. 51208043).
References
[1] W. Jiang, J. Xiao, D. Yuan, H. Lu, S. Xu, Y. Huang, Design and experiment of
thermoelectric asphalt pavements with power-generation and temperature-
reduction functions, Energy Build. 169 (2018) 39–47.
[2] J. Su, E. Schlangen, J. Qiu, Design and construction of microcapsules containing
rejuvenator for asphalt, Powder Technol. 235 (2013) 563–571.
[3] J. Gao, A. Sha, Y. Huang, Z. Liu, L. Hu, W. Jiang, D. Yun, Z. Tong, Z. Wang, Cycling
comfort on asphalt pavement: influence of the pavement-tyre interface on
vibration, J. Clean. Prod. 223 (2019) 323–341.
[4] Z. Zhang, M. Jia, W. Jiao, B. Qi, H. Liu, Physical properties and microstructures of
organic rectorites and their modified asphalts, Constr. Build. Mater. 171 (2018)
33–43.
[5] S. Hınıslıoğlu, E. Ağar, Use of waste high density polyethylene as bitumen
modifier in asphalt concrete mix, Mater. Lett. 58 (2003) 267–271.
[6] A. Fawcett, T. McNally, Blends of bitumen with various polyolefins, Polymer 41
(2000) 5315–5326.
[7] M. Fakhri, K. Hassani, A.R. Ghanizadeh, Impact of loading frequency on the
fatigue behavior of SBS modified asphalt mixtures, Procedia – Soc. Behav. Sci.
104 (2013) 69–78.
[8] M. Jasso, R. Hampl, O. Vacin, D. Bakos, J. Stastna, L. Zanzotto, Rheology of
conventional asphalt modified with SBS, Elvaloy and polyphosphoric acid, Fuel
Process. Technol. 140 (2015) 172–179.
[9] G. Polacco, A. Muscente, D. Biondi, S. Santini, Effect of composition on the
properties of SEBS modified asphalts, Eur. Polym. J. 42 (5) (2006) 1113–1121.
[10] Y. Yildirim, Polymer modified asphalt binders, Constr. Build. Mater. 21 (1)
(2007) 66–72.
[11] P. Du, H. Zhang, H. Xu, The investigation of microstructures and situ thermal
aging mechanism of organic rectorite modified bitumen, Petrol. Sci. Technol.
32 (6) (2014) 745–752.
[12] J. Wang, X. Zheng, W. Hao, N. Xu, X. Pan, Synthesis of hyper-branched
quaternary ammonium salt and its application into montmorillonite, Powder
Technol. 221 (2012) 80–89.
[13] M. Jia, Z. Zhang, L. Wei, X. Wu, X. Cui, H. Zhang, W. Lv, Q. Zhang, Study on
properties and mechanism of organic montmorillonite modified bitumens:
view from the selection of organic reagents, Constr. Build. Mater. 217 (2019)
331–342.
[14] Z. Chen, H. Zhang, C. Zhu, B. Zhao, Rheological examination of aging in bitumen
with inorganic nanoparticles and organic expanded vermiculite, Constr. Build.
Mater. 101 (2015) 884–891.
[15] H. Zhang, C. Zhu, B. Tan, C. Shi, Effect of organic layered silicate on
microstructures and aging properties of styrene–butadiene–styrene
copolymer modified bitumen, Constr. Build. Mater. 68 (2014) 31–38.
[16] S. Pavlidou, C. Papaspyrides, A review on polymer–layered silicate
nanocomposites, Prog. Polym. Sci. 33 (12) (2008) 1119–1198.
[17] G. Liu, S.P. Wu, M. van de Ven, J.Y. Yu, A. Molenaar, Structure and artificial
ageing behavior of organo montmorillonite bitumen nanocomposites, Appl.
Clay Sci. 72 (2013) 49–54.
[18] H. Zhang, J. Yu, S. Wu, Effect of montmorillonite organic modification on
ultraviolet aging properties of SBS modified bitumen, Constr. Build. Mater. 27
(1) (2012) 553–559.
10 M. Jia et al. / Construction and Building Materials 227 (2019) 116624
[19] X. Tie, C. Yan, L. Zhou, C. Liang, J. Zai, Utilize rectorite to prepare porous plates
Si/C anode materials, Electron. Compon. Mater. (China) 37 (1) (2018) 40–44.
[20] M. Vargas, L. Moreno, R. Montiel, O. Manero, H. Vázquez, Effects of
montmorillonite (Mt) and two different organo-Mt additives on the
performance of asphalt, Appl. Clay Sci. 139 (2017) 20–27.
[21] H. Zhang, C. Zhu, K. Yan, J. Yu, Effect of rectorite and its organic modification on
properties of bitumen, J. Mater. Civil Eng. 27 (8) (2015) 5.
[22] J. Yu, X. Zeng, L. Wang, S. Wu, T. Gao, Effect of organo-modified rectorite on
dynamic rheological properties of asphalt, Polym. Mater. Sci. Eng. 23 (5)
(2007) 190–193.
[23] F. Chang, S. Wu, Y. Tao, J. Wang, H. Tong, Preparation and properties of
rectorite modified asphalt, J. Wuhan Univ. Technol. (China) 29 (9) (2007) 35–
37.
[24] H. Zhang, C. Shi, J. Han, J. Yu, Effect of organic layered silicates on flame
retardancy and aging properties of bitumen, Constr. Build. Mater. 40 (2013)
1151–1155.
[25] H. Zhang, B. Tan, H. Xu, K. Yan, Microstructures and thermal aging properties of
layered silicate modified bitumens, Petrol. Sci. Technol. 32 (14) (2014) 1697–
1703.
[26] H. Zhang, H. Xu, X. Wang, J. Yu, Microstructures and thermal aging mechanism
of expanded vermiculite modified bitumen, Constr. Build. Mater. 47 (2013)
919–926.
[27] J. Liu, Y. Sun, W. Wang, J. Chen, Using the viscoelastic parameters to estimate
the glass transition temperature of asphalt binders, Constr. Build. Mater. 153
(2017) 908–917.
[28] Z. Chen, J. Pei, T. Wang, S. Amirkhanian, High temperature rheological
characteristics of activated crumb rubber modified asphalts, Constr. Build.
Mater. 194 (2019) 122–131.
[29] S. Ren, M. Liang, W. Fan, Y. Zhang, C. Qian, Y. He, J. Shi, Investigating the effects
of SBR on the properties of gilsonite modified asphalt, Constr. Build. Mater. 190
(2018) 1103–1116.
[30] H. Zhang, Z. Chen, G. Xu, C. Shi, Evaluation of aging behaviors of asphalt
binders through different rheological indices, Fuel 221 (2018) 78–88.
[31] V. Vignali, F. Mazzotta, C. Sangiorgi, A. Simone, C. Lantieri, G. Dondi,
Incorporation of rubber powder as filler in a new dry-hybrid technology:
rheological and 3D, DEM Mastic Performan. Eval., Mater. (Basel) 9 (10) (2016).
[32] A. Tanakizadeh, G. Shafabakhsh, Viscoelastic characterization of aged asphalt
mastics using typical performance grading tests and rheological-
micromechanical models, Constr. Build. Mater. 188 (2018) 88–100.
[33] J. Liu, K. Yan, J. Liu, Rheological properties of warm mix asphalt binders and
warm mix asphalt binders containing polyphosphoric acid, Int. J. Pavement
Res. Technol. 11 (5) (2018) 481–487.
[34] J. Gao, H. Wang, Z. You, M.R. Mohd Hasan, Research on properties of bio-
asphalt binders based on time and frequency sweep test, Constr. Build. Mater.
160 (2018) 786–793.
[35] D. Sun, G. Sun, Y. Du, X. Zhu, T. Lu, Q. Pang, S. Shi, Z. Dai, Evaluation of
optimized bio-asphalt containing high content waste cooking oil residues, Fuel
202 (2017) 529–540.
[36] C. Zhu, G. Xu, H. Zhang, F. Xiao, S. Amirkhanian, C. Wu, Influence of different
anti-stripping agents on the rheological properties of asphalt binder at high
temperature, Constr. Build. Mater. 164 (2018) 317–325.
[37] V. Vignali, F. Mazzotta, C. Sangiorgi, A. Simone, C. Lantieri, G. Dondi,
Rheological and 3D DEM characterization of potential rutting of cold
bituminous mastics, Constr. Build. Mater. 73 (2014) 339–349.
[38] Y. Sun, W. Wang, J. Chen, Investigating impacts of warm-mix asphalt
technologies and high reclaimed asphalt pavement binder content on rutting
and fatigue performance of asphalt binder through MSCR and LAS tests, J.
Clean. Prod. 219 (2019) 879–893.
[39] L. Zhang, C. Xing, F. Gao, T.-S. Li, Y.-Q. Tan, Using DSR and MSCR tests to
characterize high temperature performance of different rubber modified
asphalt, Constr. Build. Mater. 127 (2016) 466–474.
[40] C. Fang, R. Yu, Y. Zhang, J. Hu, M. Zhang, X. Mi, Combined modification of
asphalt with polyethylene packaging waste and organophilic montmorillonite,
Polym. Test. 31 (2) (2012) 276–281.
[41] J. Jin, Y. Tan, R. Liu, F. Lin, Y. Wu, G. Qian, H. Wei, J. Zheng, Structure
characteristics of organic bentonite and the effects on rheological and aging
properties of asphalt, Powder Technol. 329 (2018) 107–114.
[42] S. Liu, S. Zhou, Y. Xu, Evaluation of cracking properties of SBS-modified binders
containing organic montmorillonite, Constr. Build. Mater. 175 (2018) 196–
205.
[43] AASHTO, Standard Specification for Performance-Graded Asphalt Binder Using
Multiple Stress Creep Recovery (MSCR) Test. AASHTO MP19, Washington, DC.