Construction and Building Materials 177 (2018) 252–260

Contents lists available at ScienceDirect

Construction and Building Materials

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

Effect of cement on the demulsifying behavior of over-stabilized asphalt

emulsion during mixing
Jian Ouyang a,⇑, Lijun Hu a, Hongyan Li b, Baoguo Han b
a
School of Transportation and Logistics, Dalian University of Technology, Dalian, China
b
School of Civil Engineering, Dalian University of Technology, Dalian, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t
2+

Effect of pH value and Ca on the
rheological properties of asphalt
emulsion are studied.

The mixing stability of asphalt
emulsion with cement and limestone
is studied.

The demulsifying behavior of asphalt
emulsion with cement and limestone
is discussed.

The direct asphalt droplet adhesion
on cement is dominated during
mixing.

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

Article history: Over-stabilized asphalt emulsion is normally used in cement asphalt emulsion (CA) composites. The mix-
Received 7 October 2017 ing stability of asphalt emulsion with cement is vital to the workability and mechanical properties of CA
Received in revised form 14 May 2018 composites. However, the effect of cement on the demulsifying behavior of asphalt emulsion during mix-
Accepted 15 May 2018
ing is not clearly understood. To reveal the demulsifying behavior, effect of pH value and Ca2+ on the rhe-
ological properties and mixing stability of over-stabilized asphalt emulsion are studied. Results indicate
that cationic emulsions have no obvious change in the tested pH value and Ca2+ concentration range. Ca2+
Keywords:
ion is very harmful to the chemical stability of anionic emulsion. There are three stages in the demulsi-
Cement
Asphalt emulsion
fying process of pure emulsion: (1) small asphalt droplet coalescence along with trapped water; (2)
Demulsifying behavior trapped water diffuses out from coalesced asphalt droplets; (3) complete demulsification. There are
Mixing stability two demulsifying behaviors when asphalt emulsion is mixed with fine solid. One is asphalt droplet coa-
lescence, which is dominant in the mixing with limestone powder. The other is the direct droplet adhe-
sion on solid surface, which is dominated in the mixing with cement. This difference is due to that the
adsorption ability of cement is much stronger than that of limestone powder. The ions of OH and
Ca2+ released by cement hydration cannot greatly destabilize asphalt emulsion. However, emulsions with
better resistance to the invasion of OH and Ca2+ still have a better mixing stability. Therefore, reducing
the adsorption ability of cement and increasing the resistance of emulsions to hydrate ions can improve
the mixing stability of asphalt emulsion with cement.
Ó 2018 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: ouyangjian@dlut.edu.cn (J. Ouyang).

https://doi.org/10.1016/j.conbuildmat.2018.05.141
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260
1. Introduction
Cement asphalt emulsion (CA) composites are very promising
materials suitable for many applications. In the road industry, cold
mix asphalt and cold recycling asphalt mixtures are more preferred
than hot mix asphalt in pavement maintenance and repair due to
the low energy consumption and atmospheric emission of asphalt
emulsion [1–3]. In the ballastless slab track of high-speed railway,
grouting cement asphalt emulsion mortar (hereinafter abbreviated
CA mortar) has been greatly appreciated as the elastic cushion and
even-adjusting layer between slab track and concrete base because
of its good damping effect and high workability [4,5]. In all these
composite materials, asphalt and cement are both considered as
binders, thus these composite materials can be combined with
the merits of cement (high strength) and asphalt (good flexibility)
to be good semi-flexible materials [6–8]. The temperature sensitiv-
ity of CA composites can be greatly improved compared to asphalt
mixture, and the ductility becomes much better than pure cement-
based materials [6–8]. Besides, asphalt emulsion is a low-viscosity
aqueous emulsion at room temperature. It can be mixed well with
other water-based binder like cement [9]. This property ensures
that CA composites have a good workability at room temperature.
Theoretically, CA composites are more advantageous than
cement-based materials and asphalt-based materials. However,
there are still scores of challenges in the application of CA compos-
ites. A crucial issue in CA systems is the mixing stability of asphalt
emulsion. Asphalt emulsion is inherently unstable. It is easily
demulsified in or after mixing with other materials, especially for
cement due to its fine size and high reactivity. The poor mixing sta-
bility of asphalt emulsion with cement not only degrades the con-
structability of CA composites, but also affects the mechanical
properties of CA composites. For grouting CA mortar, the high
flowability may be suddenly lost during mixing due to the inade-
quate mixing stability of asphalt emulsion [10]. For cold mix
asphalt and cold recycling asphalt mixture, aggregate coating is
vital to their mechanical properties [11]. Due to inadequate mixing
stability, asphalt emulsion may quickly separate from water during
mixing and cannot fully coat aggregates [11]. Besides, the quickly
demulsified asphalt does not adhere to aggregate because of a
water-rich phase between demulsified asphalt film and aggregate,
and the trapped water in asphalt is more difficult to squeeze out
than free water [12]. As a result, poor mechanical properties are
obtained.
Even though asphalt emulsion has not strong demulsifying
behavior during mixing, asphalt emulsion with good mixing stabil-
ity is still beneficial to the workability and mechanical properties
of CA composites [10]. Improvement in the mixing stability of
asphalt emulsion can reduce the water to cement ratio of CA paste
at the same viscosity, which may be beneficial to the mechanical
properties of hardened CA paste [10]. Improvement in the mixing
stability of asphalt emulsion reduces the initial viscosity of CA
paste [10,13], which can retard the demulsification process of
asphalt emulsion and prolong the workable time of CA paste
[13]. That is why over-stabilized asphalt emulsions with high
dosage of emulsifier are generally recommended for CA mortar
[14,15]. Nowadays, over-stabilized asphalt emulsions with high
dosage of emulsifier are also preferred in cold mix asphalt and cold
recycling asphalt mixtures in China [16].
Extensive studies have been performed on the interaction
between asphalt emulsion and cement in CA paste at fresh state
in recent years. On the one hand, asphalt emulsion has a strong
retarding effect on cement hydration that is related to emulsion
type, emulsion dosage, and emulsifier type [17–19]. On the other
hand, cement hydration, which changes the properties of a CA
system (e.g., pH value and ion concentration) [20], induces
253
demulsification and accelerates the demulsifying rate. Thus, the
variation of the fresh properties (e.g. viscosity and flowability) of
CA paste is mainly related to the demulsification of asphalt emul-
sion [13]. The adsorption behavior between cement particles and
asphalt droplets, the variations of droplets morphology and droplets
size distribution are three main physical changes of asphalt droplets
in demulsification, which all affect the viscosity of CA paste [13,21].
Therefore, viscosity can be used as an index of the demulsifying
behavior in CA paste [10,13,21–23]. In fact, viscosity is usually used
as an index of the physical properties of asphalt emulsion [24–27].
The function of emulsifier is to emulsify asphalt and prevent
coalescence of asphalt droplets once formed. Therefore, the mixing
stability of asphalt emulsion with cement is controlled by emulsi-
fier [28,29] and in particular by the interaction between cement
and emulsifier. There are three main effects when cement is added
into asphalt emulsion. The first one is the change of pH value,
which may be great harmful to the stability of most cationic emul-
sifiers [9,30]. The second one is hydrate ions, mainly Ca2+, can
interact with emulsifiers and induce precipitation [20,22]. Previous
studies indicate that Ca2+ reduces the Zeta potential of anionic
emulsion [20] and makes anionic emulsifier insoluble in aqueous
solution [20,22,31]. The last phenomenon of concern is the adsorp-
tion behavior between cement and emulsifier when cement is
added to asphalt emulsion. Emulsifier is essentially a surfactant
whose molecular structure is similar to superplasticizer. Both anio-
nic and cationic emulsifiers can be adsorbed by cement and change
the rheological properties of cement paste [14,15,32,33], which can
destabilize asphalt emulsion [21].
Although the mechanisms and factors influencing the mixing
stability of asphalt emulsion are known when cement is added,
there are still many issues that are unclear. Firstly, the previous
emulsions used in the analysis on the interaction between asphalt
emulsion and cement were usually traditional slow-setting emul-
sions in which emulsifier dosage is less than 2% [9,34]. However,
over-stabilized asphalt emulsions with high emulsifier dosage are
now more preferred not only in CA mortar, but also in cold mix
asphalt and cold recycling asphalt mixtures in China [16]. Due to
high emulsifier dosage and special chemical compositions of emul-
sifier, over-stabilized asphalt emulsions have significantly different
demulsifying behavior compared to traditional slow-setting emul-
sions. Secondly, most previous studies were based on one charge
type of asphalt emulsion, and believed that anionic emulsion has
better mixing stability than cationic emulsion [22,31] due to the
aqueous alkaline environment caused by cement hydration. How-
ever, both cationic and anionic asphalt emulsion are utilized in dif-
ferent types of CA composite, and the mixing stability is not fully
dependent on emulsifier charge type. Thirdly, and also the most
important, the demulsifying behavior of asphalt emulsion in the
mixing with cement is unclear. There are two mechanisms pro-
posed to explain the demulsifying behavior when asphalt emulsion
is mixed a solid [35,36]. The first one concerns the emulsifier
adsorption on the solid surface followed by the droplet coalescence
produced by the reduction of the overall electric repulsion and fur-
ther adhesion on the solid surface (Fig. 1(a)) [35,36]. However, if
the desorption kinetics of the emulsifier from the interface is a
slow process compared with the emulsifier adsorption kinetics
onto the solid surface, the direct droplet adhesion on the solid sur-
face could be the predominant mechanism, and then droplets are
coalesced (Fig. 1(b)) [35]. The first mechanism is usually used to
explain the demulsifying process of asphalt emulsion mixed with
a solid [9,13]. However, some researchers suggested that the
demulsifying process of asphalt emulsion in CA paste was essen-
tially the direct droplet adhesion on cement surface [21]. The
demulsifying behavior of asphalt emulsion in the mixing with
cement should be further studied.
254 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260

Fig. 1. Mechanism of the demulsifying behavior of asphalt emulsion mixed with solid [35]: (a) Emulsifier desorption and further droplet coalescence; (b) Direct droplets
adsorption on solid surface.

Because of the above reasons, this study aims to study the effect
13
of the main changes (e.g., pH value and Ca2+) induced by cement
hydration on the mixing stability of over-stabilized asphalt emul- 12
sion, and also to analyze the demulsifying behavior of over-
11
stabilized asphalt emulsion mixed with cement. With this purpose,
four emulsions (two cationic and anionic) were used in the analy- 10
sis. The rheology test and traditional mixing stability method of Water
pH value

9
asphalt emulsion were employed to study the demulsifying behav- Cement paste (W/C=0.6)
ior of asphalt emulsion with cement. On the basis of the results and 8 CSS-1
discussion, the main factors of cement hydration influencing the CSS-1 + Cement (AE/C=0.4, W/C=0.6)
7 CSS-1 + Cement (AE/C=1.4, W/C=1.0)
mixing stability of over-stabilized asphalt emulsions and their
6 Anionic emulsion
demulsifying behavior can be identified. ASS-1 + Cement (AE/C=0.4, W/C=0.6)
5 ASS-1 + Cement (AE/C=1.4, W/C=1.0)

2. Experimental program 4

2.1. Materials
Cement, asphalt emulsion, and limestone powder were used in the experiment.
The employed cement was rapid hardened ordinary Portland cement P.O42.5R. Four
types of slow-setting asphalt emulsions were tested, namely two cationic asphalt
emulsions (CSS-1 and CSS-2) and two anionic asphalt emulsions (ASS-1 and ASS-
2). The emulsifiers for manufacturing CSS-1 and ASS-1 were from Jinyang Road
Material Technology Development Co., Ltd. in Jiangsu, China. The emulsifiers for
manufacturing CSS-2 and ASS-2 were from Meadwestvaco Co. in Shanghai, China.
According to the two emulsifier manufactures’ introduction, the four commercial
asphalt emulsifiers (AE) are compound emulsifiers, which are manufactured by
mixing a main emulsifier, co-emulsifier and other auxiliaries. The main emulsifiers
for CSS-1 and CSS-2 are both amides, but the co-emulsifier and other auxiliaries of
the two cationic emulsifiers differ greatly and are not known to customers. The
main component of emulsifiers for ASS-1 and ASS-2 are both benzene sulfonate,
and the co-emulsifier and other auxiliaries in them are also different. The solid con-
tents of the employed emulsifiers for CSS-1, ASS-1, CSS-2 and ASS-2 are 83.7%,
87.5%, 51.1%, and 41.7%, respectively. The effect of four emulsifiers on cement
was studied in the authors’ previous study [14]. Emulsifier dosage and solid content
in four emulsions are 3.5% and 60%, respectively. The pH values of the tested emul-
sions measured by pH meter with pH combination electrode are 3.58 (CSS-1), 3.42
(CSS-2), 13.21 (ASS-1) and 12.78 (ASS-2), respectively. Before test, cement, lime-
stone powder, and asphalt emulsion should pass the sieve of 0.15 mm.
2.2. Experimental design
Before studying the effect of pH value and Ca2+ concentration on the mixing sta-
bility of asphalt emulsion, the pH values change of asphalt emulsions (CSS-1 and
ASS-1) mixed with cement was monitored, which is shown in Fig. 2. As can be seen
from Fig. 2, no matter which emulsion types and emulsion dosages are used, the pH
values of emulsions are rapidly changed to above 12 with the addition of cement.
The pH value of ASS-1 is 13, which is nearly equal to that of cement paste. However,
the pH value of CSS-1 is 3.6. Therefore, the addition of cement can significantly
change the pH value of cationic emulsion but have nearly no effect on that of anio-
nic emulsion. The pH values of emulsions are between 12 and 13, so it can be
deduced that the OH concentration is between 0.01 and 0.1 mol/L. Because the
OH is mainly provided by the cement hydrate Ca(OH)2, the Ca2+ concentration
0 5 10 15 20
Time (min)
Fig. 2. Change of pH values of emulsions mixed with cement (AE/C and W/C are the
abbreviation of asphalt emulsion to cement mass ratio and water to cement mass
ratio, respectively).
can be calculated according to the ionization equation of Ca(OH)2 (Eq. (1)). Based
on Eq. (1), the Ca2+ concentration in emulsions is between 0.005 and 0.05 mol/L
when cement is added.
CaðOHÞ2 ! Ca2þ þ 2OH ð1Þ
Based on the above analysis, the effect of pH value was tested only for cationic
emulsions. Cationic emulsions with three pH values (original pH, 7–8, and 12–13)
were prepared. The pH value of cationic emulsion was adjusted by NaOH powder.
The effect of Ca2+ concentration was tested for all emulsions, and four Ca2+ concen-
trations (0, 0.01, 0.1, 1 mol/L) were prepared by adding CaCl2.
2.3. Test methods
2.3.1. Rheology test
The rheology test was to study the effect of pH value and Ca2+ concentrations on
asphalt emulsion. A coaxial cylinder rheometer as shown in Fig. 3 was used for test.
The diameter of the used rotor is 26.657 mm. The gap between the rotor and cylin-
der is 1.13 mm. A shear protocol as shown in Fig. 4 was performed in the rheology
test. First, a 2 min pre-shear at 300 s1 and 2 min rest were intended to create uni-
form condition before testing. Then, 9 steps, in which shear rate decreased from
100 s1 to 1 s1, were performed to get the apparent viscosity at steady state. All
samples were tested thrice. The test temperature was controlled at 22 ± 0.1 °C.
2.3.2. Traditional mixing stability test
The mixing stability test of asphalt emulsion with cement was performed
according to the Chinese standard JTG E20-2011 [37]. The test processes were as
follows. Firstly, asphalt emulsion should be diluted to 50% of solid content by deion-
ized water. Secondly, 50 g of cement and 50 g of diluted asphalt emulsion were
weighed, respectively, and then they were mixed and stirred together for 2 min
 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260 255

m
Pr ¼ ð2Þ
m1 þ m2

where Pr is the residues content; m is the mass of residues; m1 and m2 is the mass of
cement and asphalt dosage, respectively.
The same test protocol was used to study the mixing stability of asphalt emul-
sion with limestone powder. In the test of the mixing stability of asphalt emulsion
with limestone powder, the effect of pH value and Ca2+ concentration were consid-
ered. For example, limestone powder and CaCl2 powder were mixed together with
asphalt emulsion to study the effect of Ca2+ concentration on the mixing stability of
asphalt emulsion with inactive solid particles.

3. Results

3.1. Effect of pH value on the rheological properties of asphalt

emulsion

The rheological properties of cationic emulsions with different

pH values are shown in Fig. 6. It can be seen that the apparent vis-
cosity of CSS-1 changes little when pH value is between 3.58 and
Fig. 3. Rheometer employed in the rheology test. 8.6. This indicates that CSS-1 does not have an obvious change
when acidic aqueous medium is switched to neutral condition.
When the pH value rises to 12.55, the apparent viscosity of CSS-1
at low shear rate decreases but it increases at high shear rate
300
(100 s1). CSS-2 has a similar trend, but the effect of pH value is
Pre-shear for 120s more pronounced. The apparent viscosity of CSS-2 decreases at
250 low shear rate and increases at high shear rate when pH values
rises from 3.37 to 7.85. This indicates that CSS-2 has a certain inter-
Shear rate(1/s)

200 nal change from acidic to neutral environment. When pH value

rises from 7.85 to 12.58, the apparent viscosity of CSS-2 increases
150 100 s-1, 30s at low shear rate and decreases at high shear rate. The amplitude of
variation on the apparent viscosity of CSS-2 is larger than that of
100 CSS-1. Overall, both cationic emulsions are affected when pH value
Shear step reaches the value of cement paste, and the resistance of CSS-1 to
50 rest for 120s pH value change is better than that of CSS-2.

0 3.2. Effect of Ca2+ concentration on the rheological properties of

0 100 200 300 400
Time(s)
Fig. 4. Shear method about the viscosity of samples.
at a shear rate of 120r/min. Thirdly, 150 mL of deionized water was added and then
stirred for 3 min at 60r/min. At last, a filtration method was performed to evaluate
the mixing stability of asphalt emulsion. A test photo is shown in Fig. 5. The mixture
was diluted with deionized water and then filtered by a filter screen of 1.18 mm
several times. The residues above filter screen were dried by an oven and then
measured. The residues content was calculated by Eq. (2) to evaluate the mixing
stability of asphalt emulsion.
500 asphalt emulsion
The rheological properties of emulsions with different Ca2+ con-
centrations are shown in Fig. 7. It can be seen from Fig. 7 that the
apparent viscosity of CSS-1 decreases little at low shear rate and
increases very slightly at high shear rate as Ca2+ concentration
increases. CSS-2 has a similar trend, but the apparent viscosity of
CSS-2 at low shear rate decreases significantly when Ca2+ concen-
tration rises from 0.1 to 1 mol/L. Compared to cationic emulsions,
anionic emulsions have significantly different trend. With the
increasing Ca2+ concentration from 0 to 0.01 mol/L, the apparent
viscosity of ASS-1 decreases little at low shear rate and increases
very slightly at high shear. However, the apparent viscosity of
ASS-1 increases significantly no matter at low or high shear rate
when Ca2+ concentration rises to 0.1 mol/L. When Ca2+ concentra-
tion continually increases to 1 mol/L, the apparent viscosity of ASS-
1 decreases sharply. Especially at low shear rate, a value lower than
the original one is observed. Compared to ASS-1, the effect of Ca2+
on ASS-2 is more pronounced. With the addition of Ca2+ at
0.01 mol/L, the apparent viscosity of ASS-2 increases significantly,
and then ASS-2 is fully demulsified under the effect of Ca2+ at
0.1 mol/L. The above results indicate that cationic emulsions have
better resistance on the invasion of Ca2+ than anionic emulsion,
and the ranking of resistance is as follows: CSS-1 > CSS-2 >
ASS-1> ASS-2.

3.3. Effect of pH value on the mixing stability of asphalt emulsion with

limestone powder

The effect of pH value on the mixing stability of asphalt emul-

Fig. 5. Mixing stability test of asphalt emulsion. sion with limestone powder is shown in Fig. 8. It can be seen from
256 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260

pH3.58 pH3.37
1 pH8.6 1 pH7.85
pH12.55 pH12.58

Apparent viscosity(Pa·s)
Apparent viscosity(Pa·s)

0.1 0.1

0.01 0.01
1 10 100 1 10 100
Shear rate(1/s) Shear rate(1/s)
(a) CSS-1 (b) CSS-2
Fig. 6. Effect of pH value on the rheological properties of cationic emulsions.

0mol/L 0mol/L
1 0.01mol/L 1 0.01mol/L
0.1mol/L
Apparent viscosity (Pa·s)
0.1mol/L
Apparent viscosity (Pa·s)

1mol/L 1mol/L

0.1 0.1

0.01 0.01
1 10 100 1 10 100
Shear rate (1/s) Shear rate (1/s)
(a) CSS-1 (b) CSS-2
1
0mol/L 0 mol/L
1 0.01mol/L 0.01 mol/L
0.1mol/L
Apparent viscosity (Pa·s)

Apparent viscosity(Pa·s)

1mol/L

0.1
0.1

0.01 0.01
1 10 100 1 10 100
Shear rate (1/s) Shear rate(1/s)
(c) ASS-1 (d) ASS-2
Fig. 7. Effect of Ca2+ concentration on the rheological properties of cationic emulsions.

Fig. 8 that the residues content above a filter screen of 1.18 mm
increases slightly for both cationic emulsions as pH value
increases. However, the residues content is very small (below
0.2%) for all samples. This means that the two employed cationic
emulsions have a good mixing stability with limestone powder
even though pH value is higher than 12.
3.4. Effect of Ca2+ concentration on the mixing stability of asphalt
emulsion with limestone powder
The effect of Ca2+ concentration on the mixing stability of
asphalt emulsion with limestone powder is shown in Fig. 9. It
can be seen from Fig. 9 that the residues content increases slowly
for both cationic emulsions as Ca2+ concentration increases from
0 to 0.1 mol/L, and then decreases slightly with Ca2+ concentra-
tion from 0.1 to 1 mol/L. Compared to CSS-2, the residues content
of CSS-1 is smaller when Ca2+ is added. Therefore, CSS-1 has bet-
ter resistance on the invasion of Ca2+ than CSS-2. Compared to
cationic emulsion, the residues content has different trend for
anionic emulsion when Ca2+ is added. The residues content is
equal to zero for both anionic emulsions without Ca2+ and
increases slightly with the increasing Ca2+ concentration from 0
to 0.1 mol/L. However, a sharp increase in the residues content
for both anionic emulsions is observed when Ca2+ concentration
reaches 1 mol/L. Therefore, both anionic emulsions have a good
stability with limestone powder when Ca2+ concentration is lower
 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260 257

0.5 7 CSS-1
CCS-1
CSS-2
CSS-2 6 ASS-1
0.4 ASS-2
Residue content (%)

Residues content (%)

5

0.3 4

3
0.2
2
0.1
1

0.0 0
3-4 8-9 12-13 Emusion types
pH value
Fig. 10. The mixing stability of asphalt emulsion with cement.
Fig. 8. The mixing stability of cationic emulsions with limestone powder under
different pH value. viscosity at low shear rate is higher [35]. The demulsifying behav-
ior of pure emulsion is essentially droplet coalescence [9]. Droplets
with smaller size are more easily coalesced than those with larger
3.0 size [9]. Besides, a small fraction of water is usually trapped along
CSS-1
with the coalescence of asphalt droplets [9]. Based on these theo-
CSS-2
2.5 ries, the internal variation of asphalt droplets about the employed
ASS-1
four emulsions under different pH values and Ca2+ concentrations
ASS-2
Residue content (%)

can be interpreted based on the rheological properties of asphalt

2.0
1.5
1.0
0.5
0.0
0 0.01 0.1
Ca2+ concentration (mol/L)
Fig. 9. The mixing stability of emulsions with limestone powder under different
Ca2+ concentration.
than 0.1 mol/L but have a bad stability at 1 mol/L of Ca2+
concentration.
3.5. The mixing stability of asphalt emulsion with cement
The mixing stability of four asphalt emulsions with cement is
shown in Fig. 10. It can be seen from Fig. 10 that the residues con-
tent differs greatly for the employed four emulsions. The residues
content for CSS-1 is very small (near zero). The residues content
is 2.73%, 5.69%, and 6.73% for CSS-2, ASS-1 and ASS-2, respectively.
In the employed emulsions, the mixing stability of cationic
emulsions is better than that of anionic emulsions.
4. Discussion
4.1. Demulsifying behavior and mechanism of pure asphalt emulsion
According to the rheology theory of suspension, emulsion vis-
cosity is highly related to the volume fraction and size distribution
of asphalt droplets [27,38]. Increase in droplet volume fraction and
decrease in droplet size can increase emulsion viscosity [25].
Emulsion with smaller size of droplets is more thixotropic, so its
emulsion (as shown in Figs. 6 and 7).
As shown in Fig. 6(a), the apparent viscosity of CSS-1 is nearly
unchanged when pH value increases from acidic to neutral. It indi-
cates that nearly no asphalt droplet coalescence occurs in CSS-1.
With the continually increasing pH value, the apparent viscosity
of CSS-1 at low shear rate decreases. This indicates that droplets
with small size are coalesced. However, the apparent viscosity of
CSS-1 at high shear rate increases. It is due to that a small fraction
of water is trapped along with asphalt droplet coalescence [9]. This
effect can increase the efficient droplet volume fraction so that the
1 apparent viscosity at high shear rate increases. The phenomenon,
which the apparent viscosity of asphalt emulsion decreases at
low shear rate but increases at high shear rate, is observed in most
of emulsions in Figs. 6 and 7. It indicates that small asphalt droplet
coalescence along with trapped water is a typical demulsifying
behavior of pure asphalt emulsion.
Except for the above phenomenon, the phenomenon, which the
apparent viscosity of asphalt emulsion at low shear rate decreases
firstly, and then increases (for CSS-2 shown in Fig. 6(b)), and finally
decreases (for ASS-1 shown in Fig. 7(c)), is also observed. This phe-
nomenon can be interpreted by the following reasons. For CSS-2,
an increase in the apparent viscosity at low shear rate is observed
when pH value increases from 7.85 to 12.58. This phenomenon
may be due to that some trapped water is diffused out. Because
the pH value is adjusted by NaOH powder, Na+ concentration
increases with the increasing pH value so that the osmotic pressure
of aqueous phase increases. As a result, trapped water escapes
from asphalt more easily [9]. A similar phenomenon is observed
in Fig. 9 that the residues content of cationic emulsion mixed with
limestone powder decreases with the increasing Ca2+ concentra-
tion from 0.1 to 1 mol/L. For this reason the size of asphalt droplets
with trapped water decreases and the volume fraction of small
asphalt droplets increases. As a result, the apparent viscosity of
CSS-2 increases at low shear rate but slightly decreases at high
shear rate. For ASS-1, a significant increase in the apparent viscos-
ity at Ca2+ concentration of 0.1 mol/L is due to a pronounced
demulsifying behavior. A great many asphalt droplets are
coalesced and meanwhile plenty of water is trapped. As a result,
the efficient volume fraction of asphalt droplets increases
258 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260
significantly. However, the trapped water is diffused out with the
increasing Ca2+ concentration due to the increasing osmotic pres-
sure of aqueous phase [9], and the apparent viscosity of ASS-1
decreases accordingly. For ASS-1, a similar demulsifying behavior
is observed when Ca2+ concentration is 0.01 mol/L. However,
ASS-1 is fully demulsified with the increasing Ca2+ concentration.
Therefore, there are three deduced demulsifying behaviors
regarding pure asphalt emulsion which are illustrated in Fig. 11:
(1) small asphalt droplet coalescence along with trapped water;
(2) trapped water diffuses out from coalesced asphalt droplets;
(3) complete demulsification (or breaking). The three demulsifying
behaviors are also three stages in the demulsification process of
emulsions [9]. The second stage can be observed when asphalt
emulsion is not fully demulsified, such as CSS-2 and ASS-1. It can
be also seen from Figs. 6 and 7 that the change of pH value caused
by cement hydration cannot greatly destabilize the employed
cationic emulsions. This is because the employed commercial slow
setting cationic emulsifier in over-stabilized emulsion usually has
high emulsifier dosage and also a certain amount of non-ionic
emulsifier in itself, thus the repulsive force between droplets is lit-
tle affected by the invasion of alkaline ions. Besides, some cationic
emulsifier types, such as quaternary ammonium compounds, do
not react with acids and alkalis [9], which may be as co-
emulsifier in these cationic emulsifiers [9,39]. Ca2+ is harmful to
the chemical stability of anionic emulsion. This is due to that pre-
cipitation of anionic emulsifiers easily happens when Ca2+ concen-
tration is high [31].
4.2. Demulsifying behavior and mechanism of asphalt emulsion mixed
with limestone powder and cement
As mentioned in the section of Introduction, there are two
mechanisms proposed to explain the demulsifying behavior when
asphalt emulsion is mixed with solid. The first one is that asphalt
droplets are firstly coalesced and further adhered on solid surface
[35,36]. The other is the direct asphalt droplet adhesion on the
solid surface and later droplet coalescence [35]. Because limestone
powder is inactive filler and nearly does not release OH and Ca2+,
the coalescence of asphalt droplets is weak. Therefore, the residues
content above a filter screen without any addition (as shown in
Fig. 8) is mainly due to the direct droplet adhesion on the surface
of limestone powder. However, this residues content is very small,
thus the direct droplet adhesion on the surface of limestone pow-
der is also very weak. For anionic emulsion, the residues content
without Ca2+ is nearly equal to zero. Therefore, the adsorption
between asphalt droplets and limestone powder in anionic emul-
sion is weaker than that in cationic emulsion. Asphalt droplet coa-
lescence occurs with the addition of OH and Ca2+, thus the
residues content above the filter screen increases. Because Ca2+ is
harmful to the chemical stability of anionic emulsion, a strong
asphalt droplet coalescence occurs at high Ca2+ concentration.
Accordingly, the residues content for both anionic emulsions is
very high in this condition. Therefore, asphalt droplet coalescence
is a dominant demulsifying behavior in the mixing of asphalt
emulsion with limestone powder when OH and Ca2+ is added,
which is illustrated in Fig. 12(a).
Fig. 11. Illustration of the demulsifying behavior of pure emulsion.
However, the demulsifying behavior of asphalt emulsion mixed
with cement is significantly different from that of asphalt emulsion
mixed with limestone powder. As mentioned previously, the pH
value of emulsion can ranges from 12 to 13 as cement is added.
The Ca2+ concentration is between 0.005 and 0.05 mol/L, most
probably 0.01 mol/L according to previous Ref. [31]. Figs. 8 and 9
show that the residues content of asphalt emulsion-limestone
powder paste is very low in this condition. Thus, the effect of
asphalt droplet coalescence is not strong. However, the residues
content of CA paste is very high except for CSS-1 according to
Fig. 10. Therefore, a large proportion of high residues content in
CA paste is probably due to the direct droplet adhesion on cement
surface, and a small proportion of that is attributed to asphalt dro-
plet coalescence. It was previously reported that some early
cement hydrates show positive Zeta potential, such as ettringite,
monosulfate, and syngenite [40]. They can greatly adsorb anionic
surfactants, such as anionic emulsifier and superplasticizer. Port-
landite and gypsum show negative Zeta potential [40], which can
adsorb cationic emulsifier. Therefore, cement particles can adsorb
both cationic and anionic emulsifiers. Moreover, in the test method
of the mixing stability of asphalt emulsion with cement, asphalt
emulsion is directly mixed with cement. The dry cement particles,
which have a very high adsorption ability, can not only adsorb
emulsifier, but also directly adsorb asphalt droplets [41]. The
adsorption between cement and emulsifier can decrease the emul-
sifier dosage in emulsion, which can further lead to asphalt droplet
coalescence. Therefore, asphalt droplet coalescence and the
adsorption behavior between cement particles and asphalt dro-
plets are both observed in the previous studies [13,21]. In our pre-
vious work, the particle size distribution of CA paste was studied
[10,13,42]. There were two peaks corresponded to cement particles
and asphalt droplets in the particle size distribution of CA paste,
respectively. Compared to the calculated particle size distribution
of CA paste according to asphalt to cement ratio, the actual particle
size distribution of CA paste after mixing showed that the peak of
asphalt droplets slightly decreased and the peak of cement parti-
cles slightly increased [10]. Also, the peak of asphalt droplets con-
tinued to decrease and the peak of cement particles continued to
increase with time [13,42]. This phenomenon confirms the adsorp-
tion behavior between cement particles and asphalt droplets.
Meanwhile, a third peak, whose size is much larger than cement,
also occurs after 2 h [42]. This may be due to asphalt droplet coa-
lescence. Because of the high adsorption ability of cement particles,
the direct asphalt droplet adhesion on cement surface is dominant
during mixing, which is illustrated in Fig. 12(b). After mixing, both
asphalt droplet coalescence and adsorption behavior between
cement particles and asphalt droplets occur. Because there are
more components with positive Zeta potential than those with
negative Zeta potential in cement, the adsorption ability of cement
with anionic droplets is stronger than that with cationic droplets.
Therefore, the residues content for anionic emulsions is higher
than that for cationic emulsions in Fig. 10.
In summary, the ions of OH and Ca2+ released by cement
hydration cannot greatly destabilize over-stabilized asphalt emul-
sion based on the mixing stability test of asphalt emulsion with
limestone powder, but it can induce asphalt emulsion to be less
 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260
Fig. 12. Demulsifying behavior of asphalt emulsion. (a) Mixed with limestone powder with the addition of OH and Ca2+: droplet coalescence is dominated; (b) Mixed with
cement: direct droplets adsorption on cement surface is dominated.
stable according to the rheology test of asphalt emulsion. Cement
particles not only release hydration ions, but also have a strong
adsorption ability on emulsifier and asphalt droplets. The
adsorption ability of cement can lead to a strong coalescence of
asphalt droplets and the direct droplet adhesion on cement sur-
face. Therefore, both asphalt droplet coalescence and direct droplet
adhesion on cement are two important demulsifying behaviors,
but the direct droplet adhesion on cement is dominant during
mixing. Emulsions with good resistance to OH and Ca2+ invasion
have a good mixing stability. For example, CSS-1 has a better mix-
ing stability than CSS-2, and ASS-1 has a better mixing stability
than ASS-2. Besides, the mixing stability of asphalt emulsion with
cement is highly dependent on the chemical component and
dosage of emulsifier. As mentioned previously, although the pre-
cise chemical component of four emulsifiers are unknown, the
solid content of emulsifiers for CSS-1 and ASS-1 is much higher
than that of CSS-2 and ASS-2. Because of the difference in
emulsifier dosage, CSS-1 has a better mixing stability with cement
than CSS-2, and ASS-1 has a better mixing stability than ASS-2.
Because anionic emulsions have a low resistance to Ca2+ invasion
and the adsorption behavior of cement with anionic droplets is
stronger than that with cationic droplets, the employed cationic
emulsions have a better mixing stability with cement than anionic
emulsions.
Because the mixing stability of asphalt emulsion with cement is
highly dependent on the adsorption ability of cement, reducing the
adsorption ability of cement should be an efficient way to improve
the mixing stability of asphalt emulsion with cement. In the
authors’ previous studies [10,13], the mixing stability of asphalt
emulsion with cement can be greatly improved by the mixing pro-
cedure in which cement is firstly mixed with water before asphalt
emulsion is added [10]. Besides, adding superplasticizer or addi-
tional emulsifier in the premixing cement process is greatly helpful
to improve the mixing stability and prolonging the demulsification
process of asphalt emulsion [10,13]. These methods can greatly
decrease the adsorption ability of cement before asphalt emulsion
is added.
5. Conclusions
Effect of pH value and Ca2+ on the rheological properties and
mixing stability of over-stabilized asphalt emulsion were studied
to reveal the demulsifying behavior of over-stabilized asphalt
emulsion during mixing with cement in this paper. Based on the
results and discussion, the following conclusions can be drawn:
259
(1) The rheological properties of the tested over-stabilized
cationic asphalt emulsion are slightly changed by increasing
pH value and Ca2+ concentration in the tested range. How-
ever, Ca2+ concentration is very harmful to the chemical sta-
bility of over-stabilized anionic emulsion, especially when it
is higher than 0.1 mol/L. This may be due to that precipita-
tion of anionic emulsifier easily happens when Ca2+ concen-
tration is high.
(2) There are three stages in the demulsification process of pure
emulsion under the continually increasing pH value and Ca2+
concentration: (1) small asphalt droplet coalescence along
with trapped water; (2) trapped water diffuses out from coa-
lesced asphalt droplets; (3) complete demulsification. The
third stage only occurs in ASS-2 when Ca2+ concentration
is above 0.1 mol/L.
(3) There are two demulsifying behaviors when asphalt emul-
sion is mixed with fine solid. One is asphalt droplet coales-
cence. The other is the direct droplet adhesion on cement
surface. Asphalt droplet coalescence dominates in the mix-
ing of asphalt emulsion with limestone powder under the
attack of alkaline and Ca2+ ions. The direct droplet adhesion
on cement surface dominates in the mixing of asphalt emul-
sion with cement. This difference is due to that the adsorp-
tion ability of cement is much stronger than that of
limestone powder. The adsorption ability of cement with
anionic emulsions is stronger than that with cationic emul-
sions. It is probably because there are more components
with positive Zeta potential than those with negative Zeta
potential in cement.
(4) The ions of OH and Ca2+ released by cement hydration can-
not greatly destabilize over-stabilized asphalt emulsion.
However, emulsions with better resistance to the ions of
OH and Ca2+ invasion still have a better mixing stability.
Conflict of interest
The author declares that there is no conflict of interest regard-
ing the publication of this paper.
Ethical statement
The author confirms that the manuscript is not under review or
published elsewhere. The author states that the research was con-
ducted according to ethical standards.
There is no ethical concern.
260 J. Ouyang et al. / Construction and Building Materials 177 (2018) 252–260
Acknowledgements
The authors thank the funds supported from the National
Science Foundation of China (51608096), the Fundamental
Research Funds for the Central Universities (DUT17RC(4)16), and
the Doctoral Scientific Research Foundation of Liaoning Province
(201601059).
References
[1] M. Bocci, A. Grilli, F. Cardone, et al., A study on the mechanical behaviour of
cement-bitumen treated materials, Constr. Build. Mater. 25 (2) (2011) 773–
778.
[2] S. Oruc, F. Celik, M.V. Akpinar, Effect of cement on emulsified asphalt mixtures,
J. Mater. Eng. Perform. 16 (5) (2006) 578–583.
[3] Y. Niazi, M. Jalili, Effect of Portland cement and lime additives on properties of
cold in-place recycled mixtures with asphalt emulsion, Constr. Build. Mater. 23
(3) (2009) 1338–1343.
[4] J. Ouyang, Y. Tan, Rheology of fresh cement asphalt emulsion pastes, Constr.
Build. Mater. 80 (2015) 236–243.
[5] J. Ouyang, Y. Tan, D.J. Corr, S.P. Shah, The thixotropic behavior of fresh cement
asphalt emulsion paste, Constr. Build. Mater. 114 (2016) 906–912.
[6] G. Li, Y. Zhao, S.S. Pang, et al., Experimental study of cement-asphalt emulsion
composite, Cem. Concr. Res. 28 (5) (1998) 635–641.
[7] H. Song, J. Do, Y. Soh, Feasibility study of asphalt-modified mortars using
asphalt emulsion, Constr. Build. Mater. 20 (5) (2006) 332–337.
[8] X. Kong, Y. Liu, Y. Zhang, et al., Influences of temperature on mechanical
properties of cement asphalt mortars, Mater. Struct. 47 (1–2) (2014) 285–292.
[9] A. James, in: Overview of Asphalt Emulsions”, Transp. Res. Circ. EC102, Asphalt
Emulsion Technology, Washington, D. C, 2006, pp. 1–15.
[10] J. Ouyang, Y. Tan, D.J. Corr, S.P. Shah, Investigation on the mixing stability of
asphalt emulsion with cement through viscosity, J. Mater. Civil Eng. 28 (12)
(2016) 04016149.
[11] D. Swiertz, P. Johannes, L. Tashman, H. Bahia, Evaluation of laboratory coating
and compaction procedures for cold mix asphalt, J. Assoc. Asph. Paving
Technol. (2012) 81–107.
[12] D. Lesueur, C. Coupé, M. Ezzarougui, Skin formation during the drying of a
bitumen emulsion, Road Mater. Pavement 2 (2) (2001) 161–179.
[13] J. Ouyang, Y. Tan, Y. Li, et al., Demulsification process of asphalt emulsion in
fresh cement-asphalt emulsion paste, Mater. Struct. 48 (12) (2015) 3875–
3883.
[14] J. Ouyang, B. Han, Y. Cao, et al., The role and interaction of superplasticizer and
emulsifier in fresh cement asphalt emulsion paste through rheology study,
Constr. Build. Mater. 125 (2016) 643–653.
[15] J. Ouyang, H. Li, B. Han, The rheological properties and mechanisms of cement
asphalt emulsion paste with different charge types of emulsion, Constr. Build.
Mater. 147 (2017) 566–575.
[16] H. Wang, S. Li, Z. Xu, et al., Research on evaluation methods for construction
workability of emulsified asphalt cold-recycled mixture, Technol. Highway
Transp. 6 (2015) 21–26 (in Chinese).
[17] Y. Tan, J. Ouyang, J. Lv, Y. Li, Effect of emulsifier on cement hydration in cement
asphalt mortar, Constr. Build. Mater. 47 (2013) 159–164.
[18] W. Li, X. Zhu, J. Hong, W. She, P. Wang, W. Zuo, Effect of anionic emulsifier on
cement hydration and its interaction mechanism, Constr. Build. Mater. 93
(2015) 1003–1011.
[19] Z. Wang, X. Shu, T. Rutherford, B. Huang, D. Clarke, Effects of asphalt emulsion
on properties of fresh cement emulsified asphalt mortar, Constr. Build. Mater.
75 (2015) 25–30.
[20] F. Wang, Y. Liu, S. Hu, Effect of early cement hydration on the chemical
stability of asphalt emulsion, Constr. Build. Mater. 42 (2013) 146–151.
[21] S.G. Hu, T. Wang, F.Z. Wang, et al., Adsorption behaviour between cement and
asphalt emulsion in CA mortar, Adv. Cem. Res. 21 (2009) 11–14.
[22] X. Fang, A. Garcia-Hernandez, F. Winnefeld, et al., Influence of cement on
rheology and stability of rosin emulsified anionic bitumen emulsion, J. Mater.
Civil Eng. 28 (5) (2016) 04015199.
[23] X. Fang, A. Garcia-Hernandez, P. Lura, Overview on cold cement bitumen
emulsion asphalt, RILEM Technical Lett. 1 (2016) 116–121.
[24] S. Furlong, A. James, E. Kalinowski, et al., Water enclosed within the droplets of
bitumen emulsions and its relation to viscosity changes during storage,
Colloid. Surface. A 152 (1) (1999) 147–153.
[25] G.A. Nunez, G. Sanchez, X. Gutierrez, et al., Rheological behavior of
concentrated bitumen in water emulsions, Langmuir 16 (16) (2000) 6497–
6502.
[26] R.A. Mercado, J.L. Salager, V. Sadtler, et al., Breaking of a cationic amine oil-in-
water emulsion by pH increasing: Rheological monitoring to modelize asphalt
emulsion rupture, Colloid. Surface. A 458 (2014) 63–68.
[27] M. Ronald, F.P. Luis, Asphalt emulsions formulation: state-of-the-art and
dependency of formulation on emulsions properties, Constr. Build. Mater. 123
(2016) 162–173.
[28] AkzoNobel surface chemistry, Bitumen Emulsion, Technical Bulletin,
AkzoNobel, 2009.
[29] J. Sjoblom, Emulsions and Emulsion Stability, second ed., CRC Press, 2005.
[30] L. Boucard, V. Schmitt, F. Farcas, et al., Bitumen emulsions formulation and
destabilisation process relationship: influence of salts addition, Road Mater.
Pavement 16 (sup1) (2015) 330–348.
[31] X. Fang, F. Winnefeld, P. Lura, Precipitation of anionic emulsifier with ordinary
Portland cement, J. Colloid Interf. Sci. 479 (2016) 98–105.
[32] J. Plank, M. Gretz, Study on the interaction between anionic and cationic latex
particles and Portland cement, Colloid. Surface. A 330 (2) (2008) 227–233.
[33] J. Ouyang, D.J. Corr, S.P. Shah, Factors influencing the rheology of fresh cement
asphalt emulsion paste, J. Mater. Civil Eng. 28 (11) (2016) 04016140.
[34] M. Miljković, M. Radenberg, X. Fang, et al., Influence of emulsifier content on
cement hydration and mechanical performance of bitumen emulsion mortar,
Mater. Struct. 50 (3) (2017) 185.
[35] R.A. Mercado, V. Sadtler, P. Marchal, et al., Heteroflocculation of a cationic oil-
in-water emulsion resulting from Fontainebleau’s sandstone powder addition
as a model for asphalt emulsion breakup, Ind. Eng. Chem. Res. 51 (36) (2012)
11688–11694.
[36] M. Bourrel, F. Verzaro, Breaking mechanisms of asphalt emulsions for road
construction, Actualite Chimique 2–3 (1996) 42–48.
[37] Ministry of Communications of PR China. JTG E20–2011: standard test
methods of bitumen and bituminous mixtures for highway engineering.
China: China Communications Press; 2011 (in Chinese).
[38] H.A. Barnes, A Handbook of Elementary Rheology, University of Wales Institute
of Non-Newtonian Fluid Mechanics, Aberystwyth, 2000.
[39] Q. Zhang, Study on the Influence of Emulsification on the Properties of SBS
Modified Asphalts (Ph.D. thesis), Shangdong, China University of Petroleum
(East China), Qingdao, 2012 (in Chinese).
[40] J. Plank, C. Hirsch, Impact of zeta potential of early cement hydration phases on
superplasticizer adsorption, Cem. Concr. Res. 37 (4) (2007) 537–542.
[41] J. Plank, M. Gretz, Study on the interaction between anionic and cationic latex
particles and Portland cement, Colloids Surf. A: Physicochem. Eng. Asp. 330
(2008) 227–233.
[42] Y. Li, J. Ouyang, S. Wang, et al., Research on the demulsification process of
cement asphalt mortar mixture-emulsified asphalt, J. Harbin Eng. Univ. 36 (7)
(2015) 997–1000 (in Chinese).