Journal of Chemical Technology

Ayaz I. Abdullin, andA.

Elena Metallurgy, 55, 1, 2020, 73-80
Emelyanycheva

WATER-BITUMEN EMULSIONS BASED ON SURFACTANTS

OF VARIOUS TYPES

Ayaz I. Abdullin, Elena A. Emelyanycheva

Chemical Technology of Petroleum and Gas Processing Department Received 05 March 2019
Kazan National Research Technological University Accepted 31 July 2019
65 Karl Marx Str., Kazan, Russia
E-mail: emelyanycheva@gmail.com

ABSTRACT

The proper use of petroleum bitumen as a binder requires the decrease of its viscosity. It can be achieved by
melting, dissolution in hydrocarbons (diluents) and emulsification in water. Cationic emulsifiers are currently used in
production of bitumen emulsions for road construction. The study of the possibility of using surface-active substances
of other classes in order to expand the range of effective bitumen emulsifiers is an actual task. The investigation re-
ported focuses on cationic, anionic, nonionic, zwitterionic surfactants tested as emulsifiers for production of bitumen
emulsions classified as slow-setting one. The bitumen emulsions viscosity, the decomposition rate and the adhesion
to the mineral materials are determined. An increase of the bituminous emulsions decay index is observed with an
increase of the studied surfactants concentration. The viscosity of bitumen emulsions decreases with an increase of
the surfactants concentration. A transition from the class of rapid-setting bitumen emulsions to that of slow-setting
one is observed in case of emulsions based on cationic surfactants. The latter demonstrate the best adhesion proper-
ties in respect to the mineral material.
Keywords: surfactant, bitumen, emulsion, viscosity, decay index, adhesion.

INRTODUCTION emulsifiers when present in small quantities dissolve in

The proper use of petroleum bitumen as a binder
requires the decrease of its viscosity. It can be achieved
by melting, dissolving in hydrocarbons (diluents) and
by emulsifying in water [1]. The water-bitumen emul-
sions are used in a number of road construction works
including a macadam construction, a surface treatment,
a production of cold emulsion-mineral mixtures, a cold
stored mixtures production, a road pavements patching,
a laying of thin pavements protective layers [2]. Bitumen
emulsions have a number of indisputable advantages
compared to those of the classic bituminous binders used
in the hot technologies [3]. The preparation of stable
water-bitumen emulsions requires the use of special
substances called emulsifiers. Surfactants are applied as
such substances. In addition to the emulsifying action,
the surfactants stabilize the emulsions dispersion and
make them stable during a prolonged storage [4]. The
water and help to reduce the interfacial tension between
the water and the bitumen, which promotes the stable
distribution of bitumen droplets in the aqueous phase
[5]. The viscosity, the decay index, the stability, the ad-
hesion properties are among the basic properties of the
bitumen emulsions [6]. They depend on the properties
of the bitumen and the emulsifiers [7] as well as on the
emulsification mode [8, 9]. The emulsification efficiency
depends on the bitumen composition and structure, the
composition and the structure of the surfactant and the
emulsification mode [4]. If the resins to oils ratio in the
composition of the bitumen is greater than 0.6, and the
resins to asphaltenes ratio is within the range from 0.5 to
2.0, the bitumen is expected to be efficiently emulsified.
An increase of the resins content leads to an increase
of the bitumen surface activity, while an increase of the
asphaltenes content has the opposite effect [7].
Currently, the cationic emulsifiers are generally used

73
 Journal of Chemical Technology and Metallurgy, 55, 1, 2020
[10] to produce bitumen emulsions for road construc-
tion. The study of the possibility to introduce surface-
active substances of other classes as bitumen emulsions
components in order to expand the effective emulsifiers
range is the aim of the present investigation.
EXPERIMENTAL
Materials
Three road petroleum bitumen of 60/90 penetration
grade, conditionally designated as A, B, C, were used
to prepare bitumen emulsions. Their characteristics are
presented in Table 1, while their group compositions
are listed in Table 2. As evident from Table 2, the group
components ratios of the bitumens studied were within
the limits providing to predict a good emulsification.
Surfactants of various classes were studied as
emulsifiers: cationic surfactants, such as oleylami-
dopropylbenzyldimethylammonium chloride (desig-
nated as Emulsifier 1) and coco-(C12-C18) amidopropyl,
alkyl-(C12-C14) dimethylbenzylammonium chloride
(designated as Emulsifier 2); an anionic surfactant,
such as the mixture of isomers of sodium salts of alkyl
benzene sulfonic acids (designated as Emulsifier 3);
nonionic surfactants, such as ethoxylated nonylphenol
AF9-12 and ethoxylated nonylphenol AF9-9 (designated
as Emulsifier 4 and Emulsifier 5, respectively); zwit-
terionic surfactants, such as cocamidopropyl-(alkyl-)
dimethylamine oxide (designated as Emulsifier 6) and
Cocamidopropyl betaine (designated as Emulsifier 7).
Methods
The water-bitumen emulsions were obtained in a
laboratory colloidal mill - a flow-circulation device with
suction and discharge circuits. An impeller with grooves
of an oval shape driven by a motor shaft acted as its main
Table 1. Basic performance properties of bitumen 60/90.
Performance property
bitumen А
Softening point, °C
Fraas brittleness point, °C
Penetration at 25 °С, 0.1 mm
Ductility, at 25 °C, cm
74
element. On the inner surface of the flange there were
grooves, which were identical in their shape and size
to the grooves on the working disk (the impeller). The
bitumen and the water solution of the emulsifier were
thoroughly grinded and emulsified on introduction to
the space between the disk and the flange. The effect
observed was determined by the high rotation speed of
the disk and the presence of grooves on the flange and
disc surfaces. The bitumen emulsions were obtained
within 2 min at 5000 rpm - 6000 rpm. The color and
the dispersity indicated [1, 7] the completion of the
process. Furthermore, when a glass stick was immersed
in the prepared water-bitumen emulsion, the emulsion
on the stick surface should look homogeneous with a
fine-grained structure. It should be easily washed off.
Distilled water was used to prepare the bitumen emul-
sions in view of the fact that the water hardness could
lead to the emulsion breakdown. This in turn leads to
the requirement to use water whose hardness was not
exceeding 6 mg/l [2].
The laboratory tests of the quality of the prepared
bitumen emulsions were conducted one day after the
preparation of the emulsions in accordance with the
current Russian Federation standard 55420-2013. The
bitumen emulsions viscosity was characterized on the
ground of a relative value determined in accordance with
Russian Federation standard 55421 - 2013, whose main
regulations corresponded to standard EN 12846-1:2002.
The bitumen emulsion viscosity was characterized by
the efflux time of 50 ml of emulsion through a hole of a
diameter of 4 mm at a temperature value of (40 +1)°C
in an efflux viscometer. The decomposition rate and the
adhesion to the mineral material were also determined.
The decomposition rate of the bitumen emulsions was
characterized on the ground of a decay index deter-
The value
bitumen B bitumen С
54.5 53.4 45.6
-22 -21 -21
78 79 74
70 89 > 100
 Ayaz I. Abdullin, Elena A. Emelyanycheva
Table 2. A structural - group composition of bitumen 60/90.
Component
bitumen А
Asphaltenes (А), % 26.26
Oils (O), % 31.28
Resins (R), including, 42.45
Benzene resins (BR) 29.05
Alcohol-benzene resins (ABR) 13.4
R/O 1.36
R/А 1.62
(R+А)/O 2.2
mined in accordance with Russian Federation standard
55422 – 2013. Its main regulations corresponded to EN
13075-1:2002 standard. The decay index characterizing
the bitumen emulsion breaking behavior corresponded
to the mass of the mineral filler in grams necessary for
the decay of 100 g of the bitumen emulsion. The bitu-
men emulsions adhesive properties were determined in
the course of a water immersion test following Russian
Federation standard 55426 – 2013. Its main regulations
corresponded to EN 13614:2011 standard.
RESULTS AND DISCUSSION
The first step of the work was dedicated to the study
of the possibility of emulsification of petroleum road
bitumen using different classes of surfactants.
The structure and the properties of the bitumen
emulsions largely depend on the emulsifier nature [7].
Therefore, the study of the effect of new surfactants
is a very important task in further development of the
technology of petroleum bitumen emulsification.
The bitumen emulsifying ability is associated with
the complex chemical composition, the structural and
mechanical properties of the emulsion. Even nowadays
there is no general criterion for predicting whether
particular bitumen will be emulsified, as well as what
emulsifier will act as the best one. The emulsifying
ability of the bitumen should be individually studied
for each system [1].
The compositions of the studied water-bitumen
Component content, % wt.
bitumen B bitumen С
27 16.67
25.5 39.39
47.5 43.94
32.5 27.27
15 16.67
1.86 1.12
1.76 2.64
2.92 1.54
emulsions and the results of their emulsifying ability
are presented in Table. 3. The concentrations of the
surfactants range from 0.3 wt. %t to 2.0 wt. %. This is
the usual working range of concentrations of emulsifiers
finding the greatest industrial application.
The data presented in Table 3 provides to conclude
that in presence of cationic and zwitterionic surfactants
all bitumen demonstrate a good emulsifying ability.
The cationic emulsifiers are considered universal for
the preparation of water-bitumen emulsions used in the
road construction. In the presence of anionic Emulsifier 3
bitumen C cannot be emulsified. According to the data of
Table 2, the resins to asphaltenes (R/A) ratio for bitumen
C is 2.64 wt. %. It does not fit the range of 0.5 wt. % - 2
wt. % and can affect the bitumen emulsification. Stable
emulsions can be produced on the ground of bitumen A
within the entire range of concentrations of Emulsifier
3 (0.5 wt. % - 1.5 wt. %.). Bitumen A, B, C cannot be
emulsified in presence of the non-ionic Emulsifier 4 at a
surfactant concentration less than 1 wt. %. The working
concentrations of the non-ionic surfactants are in the
range from 1 wt. % up to 2 wt. %. Bitumen B cannot
be emulsified with the non-ionic surfactant Emulsifier
5 at any surfactant concentration. Bitumen A and bitu-
men B are characterized by a similar structural group
composition. However, the use of Emulsifier 5, unlike
that of Emulsifier 4, does not result in obtaining stable
bitumen emulsions. Emulsifier 4, being ethoxylated
nonylphenol like Emulsifier 5, differs from its behavior
by providing a higher degree of ethoxylation. Thus, the
75
 Journal of Chemical Technology and Metallurgy, 55, 1, 2020

Table 3. Compositions and emulsifying abilities of the bitumen emulsions prepared.

Surfactants Component content, % wt. Emulsifying ability
Bitumen Water Surfactant Bitumen Bitumen B Bitumen
60/90 А С
50 49.7 0.3 – –
50 49.5 0.5 + +
50 49.2 0.8 + +
Emulsifier 1
50 49.0 1.0 + +
50 48.5 1.5 + +
50 48.0 2.0 + +
50 49.7 0.3 + –
50 49.5 0.5 + +
50 49.2 0.8 + +
Emulsifier 2
50 49.0 1.0 + +
50 48.5 1.5 + +
50 48.0 2.0 – –
50 49.5 0.5 + –
50 49.2 0.8 + –
Emulsifier 3 50 49 1 + –
50 48.5 1.5 + –
50 49.5 0.5 – –
50 49.2 0.8 – –
50 49 1 + –
Emulsifier 4
50 48.5 1.5 + +
50 48.2 1.8 + +
50 48 2 + +
50 49.2 0.8 – –
50 49 1 – –
50 48.5 1.5 – –
Emulsifier 5
50 48.2 1.8 – –
50 48 2 – –
50 47.5 2.5 – –
50 49.7 0.3 –
50 49.5 0.5 – +
50 49.2 0.8 + +
Emulsifier 6 50 49 1 + +
50 48.5 1.5 + +
50 48.2 1.8 + +
50 48 2 + +
50 49.5 0.5 + +
50 49.2 0.8 + +
50 49 1 + +
Emulsifier 7
50 48.5 1.5 + +
50 48.2 1.8 + +
50 48 2 + +

76
 Ayaz I. Abdullin, Elena A. Emelyanycheva
emulsifying activity of the non-ionic surfactant increases
with an increase of its molecule degree of ethoxylation.
Bitumen B does not give stable bitumen emulsions with
zwitterionic Emulsifier 6 at a surfactant concentration
of 0.3 wt. % - 0.5 wt. %. The working concentrations
of this zwitterionic surfactant are in the range from 0.8
wt. % up to 2 wt. % t. Bitumen B and bitumen C can be
used with zwitterionic Emulsifier 6 to produce stable
bitumen emulsions in the entire range of surfactant
concentrations.
The estimation of the viscosity, the decay index and
the adhesion properties of the water-bitumen emulsions
is carried out during the second stage of the research.
The viscosity of the water-bitumen emulsion is one
of its most important properties. It can be changed by
various factors: by affecting the dispersion medium
viscosity, by varying the bitumen mass content of the
emulsion and by controlling the bituminous particles size
in the emulsion. The viscosity promotes the wetting of
the mineral material surface with a bitumen emulsion,
the penetration of the bitumen emulsion into the micro
cracks or the micro pores on the mineral material surface.
It also affects the emulsion decomposition rate during
its application [6].
The conventional viscosity of the bitumen emulsions
is determined at 40°C and the results are presented in
Table 4.
The data in Table 4 shows that the bitumen emulsions
viscosity decreases with an increase of the studied sur-
factants concentration. This parameter is in accordance with
the standard requirements in case of all analyzed samples.
The main operational property of the bitumen
emulsions refers to their ability to form a film of a
bituminous binder on the mineral material surface at a
fixed rate after distribution of the binder. The emulsions
break down when the dispersed phase separates from
the dispersion medium and the bituminous particles
adhere to the surface of the mineral material [1]. Three
classes of bitumen emulsions are distinguished by the
rate of decomposition (decay index) when interacting
with a stone material: rapid-setting, medium-setting and
slow-setting bitumen emulsions. The need to obtain a
bitumen emulsion of a particular class is determined by
the area of the ​​subsequent application. The decay index,
a characteristic of the breaking behavior of the bitumen
emulsions, is determined in the course of this investiga-
tion following the requirements of Russian Federation
standard 55422 - 2013.
The class of the emulsions based on bitumen A
changes with an increase of Emulsifier 1 content from a
rapid-setting to a slow-setting one. In case bitumen C is
used, all the emulsions can be classified as rapid-setting.
The class of the emulsions based on bitumen A changes
with an increase of the content of the cationic Emulsifier
2 from a rapid-setting to a slow-setting one. The emul-
sions change from a medium-setting to a slow-setting
one in case bitumen C is used. Thus, in some cases, when
cationic surfactants and bitumen of a certain structural
group composition are used, the breaking behavior of
the emulsions can be controlled by the concentration
of the surfactants. All the emulsions are characterized
by a high storage and shake stability, which increases
with an increase of the amount of the surfactants in the
emulsions.
The increase of the anionic surfactant Emulsifier 3
concentration above 1 wt. % does not lead to a signifi-
cant viscosity decrease and a decay index change. The
studied anionic water-bitumen emulsions belong to the
slow-setting class.
The nonionic surfactants do not give charged par-
ticles (ions) in solutions. They dissolve in water due to
the presence of functional groups in their molecules that
have a strong affinity for water. These emulsifiers are of
a particular interest because they are compatible with
all ionic surfactants [11]. The most important nonionic
surfactants from a practical point of view refer to the
addition products of ethylene oxide to alcohols, alkyl-
phenols, carboxylic acids, amines, and other compounds
with reactive hydrogen atoms. The emulsifying activity
of ethoxylated nonylphenols is currently studied. Bitu-
men emulsification does not occur in presence of the
nonionic surfactant Emulsifier 4 at a surfactant concen-
tration lower than 1 wt. %. The decay index increases,
and the conditional viscosity decreases with an increase
of the emulsifier concentration. The decay indexes are
high ​​at all concentrations of Emulsifier 4. All studied
nonionic water-bitumen emulsions are slow-setting. It
can be noticed that the studied nonionic water-bitumen
emulsions have a comparatively low stability during
storage and shaking. For this reason their industrial
application should be considered only in compositions
containing other surfactants. It can also be noticed, that
the nonionic Emulsifier 5, which has the lower degree
of oxyethylation among the molecules studied, does not
77
 Journal of Chemical Technology and Metallurgy, 55, 1, 2020

Table 4. Bitumen emulsions decay index and viscosity.

Surfactants Component content, % wt. Decay index, g Viscosity, s
/ 100 g
Bitumen Water Surfactant

А B С

50 49.5 0.5 154 12.14

50 49.2 0.8 199 12
50 49.0 1.0 215 11.70
50 48.5 1.5 254 11.61
50 48.0 2.0 281 11.54
Emulsifier 1 50 49.5 0.5 138 12.68
50 49.2 0.8 185 11.91
50 49.0 1.0 187 11.82
50 48.5 1.5 189 11.62
50 48 2.0 190 11.28
50 49.7 0.3 171 11.98
50 49.5 0.5 204 11.78
50 49.2 0.8 219 11.62
50 49.0 1.0 278 11.43
Emulsifier 2
50 48.5 1.5 341 11.17
49.5
50 0.5 204 11.81
50 49.2 0.8 245 11.78
50 49.0 1.0 259 11.33
50 48.5 1.5 326 11.02
50 49.5 0.5 419 12.51
50 49.2 0.8 427 11.75
Emulsifier 3
50 49.0 1.0 575 11.63
50 48.5 1.5 582 11.60
50 49 1.0 411 12.68
50 48.5 1.5 447 12.12
50 48.2 1.8 509 11.98
Emulsifier 4 50 48 2.0 511 11.27
50 48.5 1.5 471 12.74
50 48.2 1.8 476 12.57
50 48 2 606 12.24
50 49.5 0.5 258 13.97
50 49.2 0.8 338 13.09
50 49.0 1.0 386 12.90
50 48.5 1.5 453 12.12
50 48.2 1.8 468 11.71
Emulsifier 6 50 48.0 2.0 473 11.57
50 49.2 0.8 279 14.86
50 49.0 1.0 349 14.73
50 48.5 1.5 426 13.01
50 48.2 1.8 472 12.00
50 48.0 2.0 558 12.00
50 49.5 0.5 307 12.35
50 49.2 0.8 369 12.02
50 49.0 1.0 393 11.90
50 48.5 1.5 448 11.72
Emulsifier 7 50 48.2 1.8 464 11.29
50 48.0 2.0 504 11.00
50 49.5 0.5 317 12.33
50 49.2 0.8 334 11.58
50 49.0 1.0 378 11.27
50 48.5 1.5 358 11.01
50 48.2 1.8 417 11.00
50 48.0 2.0 447 11.00

78
 Ayaz I. Abdullin, Elena A. Emelyanycheva
show any emulsifying activity (Table 3). Thus, it can be
concluded, that the number of ethylene oxide molecules
attached to the molecule of the original substance defin-
ing the degree of ethoxylation, determines the emulsify-
ing activity of the nonionic surfactant.
The amphoteric surfactants contain two functional
groups, one of which is acidic, while the other one is
basic. They ionize and behave in an aqueous solution
depending on the conditions applied. In an acidic solu-
tion they tend to demonstrate properties of cationic
surfactants, while in an alkaline solution - those of
anionic surfactants. Emulsifiers of this type are desig-
nated as Emulsifier 6 and Emulsifier 7 in the present
investigation.
Table 4 shows that the value of the decay index
increases significantly with an increase of the zwit-
terionic emulsifiers’ content. Besides, all emulsions
obtained refer to the slow-setting class. The zwitterionic
water-bitumen emulsions are characterized by supersta-
bility. Their stability increases with an increase of the
surfactant concentration.
One of the main reasons for the early destruction
of the road surfaces is the poor adhesion of the binder
to the surface of the mineral material. To estimate the
adhesive properties of samples of the bitumen emul-
sions obtained, crushed limestone with a size of 5
mm to 15 mm is used for anionic bitumen emulsions
testing, while granite crushed stone of the same size is
used in all other cases. The essence of the method is to
evaluate the ability of the bitumen emulsion to coat the
surface of the mineral material and remain on it under
temperature and water presence effects. The cationic,
anionic and zwitterionic water-bitumen emulsions are
characterized by adhesive properties that correspond to
the standard requirements. Water-bitumen emulsions
containing non-ionic surfactants show unsatisfactory
results in respect to the adhesion strength. It is evident
that a good adhesive performance of the binder contain-
ing non-ionic surfactants can be obtained if the latter are
used in a combination with surfactants of another type.
CONCLUSIONS
The emulsifying possibility of petroleum road bitu-
men using surfactants of various types is studied. It is
possible to obtain stable water-bitumen emulsions on the
ground of the studied cationic, anionic and zwitterionic
surfactants. The bitumen cannot be emulsified in pres-
ence of the studied non-ionic emulsifiers at a surfactant
concentration less than 1.0 wt. %. It is also found that
the emulsifying activity of the non-ionic surfactants
increases with an increase of the degree of ethoxylation
of their molecules.
An estimation of the viscosity, the decay index and
the adhesion properties of the obtained water-bitumen
emulsions is carried out. The viscosity of the bitumen
emulsions decreases, while the decay index increases
with an increase of the concentration of the studied
surfactants. Bitumen emulsions of various rates of de-
composition (decay indexes) can be produced using the
studied cationic surfactants, while the latter concentra-
tion controls the emulsions breaking behavior. The stud-
ied anionic, nonionic and zwitterionic water-bitumen
emulsions can be classified as slow-setting bitumen
one. They are characterized by well outlined adhesive
properties corresponding to the standard requirements.
The water-bitumen emulsions containing non-ionic
surfactants show unsatisfactory results in respect to the
strength of adhesion to the mineral material. A higher
adhesive performance of the binder non-ionic surfactants
can be achieved if they are used in a combination with
surfactants of other types.
REFERENCES
1. F.V. Karpeko, A.A. Gureev, Bituminous emulsions.
Fundamentals of physical and chemical technology
of production and use, Moscow, CNIITEneftekhim,
1998, (in Russian).
2. I.N. Petukhov, Road emulsions, Minsk, EADE, 1997,
(in Russian).
3. Y. Wang, Y. Gao, Q. Zhang, Q. Meng, A novel cati-
onic emulsifier used for preparing slow-cracking and
rapid-setting asphalt: Synthesis, surface activity, and
emulsification ability, Journal of Dispersion Science
and Technology, 39, 4, 2018, 478-483.
4. J. Bibette, F. Leal-Calderon, V. Schmitt, P. Poulin,
Emulsion Science. Basic Principles. An Overview, S.
Springer Tracts in modern physics, Vol. 181, 2002.
5. K.R. Lange, Surfactants: synthesis, properties, analy-
sis, application, St. Petersburg, Profession, 2007, (in
Russian).
6. M. Ronald, F.P. Luis, Asphalt emulsions formulation:
state-of-the-art and dependency of formulation on
79
 Journal of Chemical Technology and Metallurgy, 55, 1, 2020
emulsions properties, Constr. Build. Mater., 123,
2016, 162-173.
7. V.A. Budnik, Research and development of meth-
ods for producing petroleum bitumen emulsions:
Author’s abstract, Ufa, Russia, 2009, (in Russian).
8. J.P. Gingras, P.A. Tanguy, S. Mariotti, P. Chaverot,
Effect of process parameters on bitumen emulsions,
Chem. Eng. Process., 44, 2005.
9. J.P. Gingras, P.A. Tanguy, S. Mariotti, P. Chaverot,
Effect of process parameters on bitumen emulsions,
80
Chem. Eng. Process. Process Intensif., 44, 2005,
979-986.
10. A. Yuliestyan, M. García-Morales, E. Moreno, V.
Carrera, P. Partal, Assessment of modified lignin cati-
onic emulsifier for bitumen emulsions used in road
paving, Materials & Design, 131, 2017, 242–251.
11. M.R. Idrisov, Slow-setting water-bitumen emul-
sions stabilized by compositions based on proxanols
and cationic surfactants: Author’s abstract. Kazan,
Russia, 2014, (in Russian).