Fuel Processing Technology 159 (2017) 272–279

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Fuel Processing Technology

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

Review

Development of methods improving storage stability of bitumen

modified with ground tire rubber: A review
Maciej Sienkiewicz ⁎, Kaja Borzędowska-Labuda, Artur Wojtkiewicz, Helena Janik
Polymer Technology Department, Chemical Faculty, Gdansk University of Technology, Gabriela Narutowicza Street 11/12, 80-233 Gdansk, Poland

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

Article history: The following paper presents an overview of methods for improving the storage stability at high temperature of
Received 23 June 2016 rubber modified bitumen. The storage stability of the rubber modified bitumen can be improved by using a var-
Received in revised form 27 January 2017 ious types of modifiers that form the bonds between the components of these binders. The increase in stability
Accepted 31 January 2017
can also be achieved by using crumb rubber surface-activated by furaldehyde or ground tire rubber (GTR) treated
Available online 7 February 2017
by gamma irradiation or modified by devulcanization process. The storage stability of rubber modified bitumen
Keywords:
can be also improved by preparing compositions obtained from GTR and other components leading to a reduc-
Rubber modified bitumen tion in density as compared to unmodified GTR. unmodified GTR.
Storage stability © 2017 Elsevier B.V. All rights reserved.
Ground tire rubber(GTR)

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
2. Rubber modified bitumen obtained from ground tire rubber (GTR). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
2.1. Properties of rubber modified bitumen derived from GTR. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
2.2. Interactions occurring in rubber modified bitumen obtained from GTR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
2.3. Lack of stability of rubber modified bitumen during storage at high temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
3. Methods for improving storage stability of rubber modified bitumen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
3.1. Stability of rubber modified bitumen during storage at high temperature – testing methods . . . . . . . . . . . . . . . . . . . . 274
3.2. Modifiers used to improve storage stability of rubber modified bitumen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278

1. Introduction thermoplastics and elastomers (e.g. virgin rubber or polyurethanes),

[18–20] or as a modifier of concrete [21–24] and also asphalt [25–29]
The amount of polymer wastes is increasing every year. Most of to improve the properties of these materials [30].
them are obtained from postconsumer tires [1], which are a serious en- Bitumen is a viscoelastic material which has good mechanical and
vironmental problem [2–4]. Development of research on improving rheological properties preferred for road surface. However, with the in-
methods of recovery and recycling and regulations implementing [5– creasing number of vehicles on the road, there is a need to improve the
15] the principle of extended producer responsibility in the field of life properties of the asphalts, for example, strength, fatigue, rutting, resis-
tires led to solutions that enable the transformation of rubber waste tance to aging, low temperature cracking. In order to improve the prop-
into energy or new polymer products. The progress made in recent erties of asphalt the polymers are added into the asphalt composition
years mean that ground tire rubber (GTR) came to be seen not only as [31–33]. From the economical point of view, recycled polymers are
a cheap filler, but primarily as a source of valuable raw materials [6–7, more attractive. Much of the research in the field of asphalts modified
16–17]. Ground tire rubber is commonly used as a filler in thermosets, with polymer wastes relates to the use of ground rubber from waste
tires, as a modifier of their properties [34–35]. Rubber-modified bitu-
⁎ Corresponding author. men, compared to the unmodified asphalt is characterized by improved
E-mail address: maciej.sienkiewicz@pg.gda.pl (M. Sienkiewicz). mechanical properties, in particular increased flexibility, abrasion

http://dx.doi.org/10.1016/j.fuproc.2017.01.049
0378-3820/© 2017 Elsevier B.V. All rights reserved.
 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279 273

resistance, resistance to rutting and cracking resistance at low tempera- 2.2. Interactions occurring in rubber modified bitumen obtained from GTR
tures and ability to reduce the noise during contact of tires with the
ground [36]. Despite the development of research in the field of asphalts
However, polymers-modified asphalt has a low resistance to aging modified by ground tire rubber, interactions occurring between
[37]. Due to weak physical interactions and no chemical interactions be- ground tire rubber and asphalt are not fully understood. According
tween the asphalt and polymer modifiers, polymer-modified bitumen to current knowledge, the physical interactions has a major effect
has very poor storage stability at high temperature (140–180 °C) [38]. on the properties of the rubber modified bitumen, but chemical
The modifier can be separated from the asphalt and depending on interactions are not significant. Understanding the interactions
the density of modifier molecule thereof may fall to the bottom of stor- between asphalt and granulated rubber is extremely important
age tanks or rise to the surface. As the consequence, decomposition of not only in the course of modification, but also during processing,
the polymer-asphalt binder may occur [37]. This phenomenon is caus- storage and use of binder [10,46].
ing the loss of bituminous binders properties of modified asphalt and Two phenomena are important when considering the properties of
can cause a failure of the system to transport asphalt by pipelines. asphalt binders modified by ground rubber:
Therefore bitumen modified by incompatible polymers have to be con-
• Absorption of light fractions of asphalt (aromatic oils) by ground
stantly mixed.
rubber;
The following topics are discussed in this article: interactions occur-
• Decomposition of ground rubber in asphalt.
ring in the rubber modified bitumen, stability test methods of rubber
modified bitumen and methods of modifying bitumen with rubber in
the direction of improving their stability at high temperature during Absorption of light fractions of asphalt by rubber granulate may
storage. occur during the addition of ground rubber to asphalt heated. It causes
swelling of the ground rubber and expands up to three times compared
to the original volume. This in turn decreases the distance between the
2. Rubber modified bitumen obtained from ground tire rubber grains of the rubber granulate distributed in liquid asphalt, which re-
(GTR) sults in even tenfold increase of viscosity [8,10].
Decomposition of rubber grains in asphalt occurs when the temper-
2.1. Properties of rubber modified bitumen derived from GTR ature of the asphalt modification is too high or the mixing time during
the modification is too long.
Historically speaking, the use of rubber granulate as an asphalt mod- Then, two the processes take place, such as depolymerization and
ifier for paving roads, started in the 1840s. In those days, it was made devulcanization, followed by partial disintegration and dissolution of
the first experiment involving natural rubber and asphalt. Attempts of ground rubber in liquid asphalt, which reduces the viscosity of the rub-
modifications were carried out to take advantage of the elastic proper- ber modified bitumen [8,10].
ties of natural rubber to get more wear-resistant asphalt. Since 1960,
shredded postconsumer tires are also recycled for use as a component 2.3. Lack of stability of rubber modified bitumen during storage at high
of asphalt [8]. The research led to the division of modification methods temperature
into wet and dry processes. The wet process comprises preparing a liq-
uid rubber-modified bitumen by mixing asphalt and rubber granules for The instability of the rubber modified bitumen at high temperature
at least 45 min at a temperature of 180–210 °C. The next stage is a mat- creates a serious problem in its application. The compositional hetero-
uration of rubber-modified bitumen for 3 h at 180 °C without stirring geneity of the rubber modified bitumen, as well as the difference in den-
[10]. The obtained mixture is combined with mineral aggregate. Dry sity between bitumen and rubber granulate are the reason that the
way is the introduction of granulated rubber for mineral aggregate be- rubber granulate originally evenly distributed in the rubber modified bi-
fore entering the bitumen, and then mixing all the ingredients at tumen, tends to fall to the bottom of the tanks during storage [35,38].
163 °C [39–40]. Favorable properties of road pavements are obtained The phase separation phenomenon of the rubber modified bitumen de-
using wet method. scribes Stokes' law, according to which, the settling velocity of rubber
Charles McDonald was the first person who developed a method of grains to the bottom of the tank is as follows:
modifying an asphalt rubber granules by wet process. He proved that
rubber modified bitumen is characterized by the favorable characteris- ϑ t ¼ 2α 2 ρg=9η ð1Þ
tics from both the base materials. At the same time, two Swedish com-
panies replaced part of the mineral aggregates in asphalt mixtures by where:
granulated rubber (dry process), thereby obtaining an asphalt mix • ϑt - the settling velocity of the distributed rubber granulate [m/s];
with increased resistance to the effects of the snow chains [8,41]. • α - the radius of the distributed rubber granules [m];
The GTR modified asphalt is under investigation by many re- • η - the dynamic viscosity of liquid [Pa·s];
searchers, and are widely used by manufacturers. This is because, the • Δρ - the density difference between phases (rubber granulate and
addition of GTR to asphalt contributes not only to solve the problem of bitumen) [kg/m3];
utilization of waste tires, but also affects the improvement of the me- • g - gravitational acceleration [m/s2].
chanical properties of asphalt, and consequently the durability of road
surfaces [35]. The rubber-modified bitumen, compared to the unmodi- According to Eq. (1), it can be concluded that stable rubber modified
fied binders are characterized by increased fatigue strength, resistance bitumen can be obtained by:
to rutting and low-temperature cracking. They also are characterized
by higher values of the viscosity and the softening point and a lower • decreasing the particles size of rubber granulate;
penetration values. The advantage of asphalt concrete obtained from • decreasing the density difference between rubber granulate and
the rubber-modified bitumen is also reduction of a noise resulting bitumen;
from the contact of the tire with the ground. It has been shown that • increasing the viscosity of bitumen [10].
the adhesion of the vehicle wheels to the surface of the rubber modified
asphalt is improved compared to unmodified asphalt. This shortens The instability of the rubber-modified bitumen causes difficulties in
braking distances of vehicles, and thus contributes to increased road its application. When the liquid rubber-modified bitumen is stored at
safety [29,42–45]. high temperature (about 180 °C), the rubber grains falling on the
274 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279

bottom of the tank could lead to clogging of the drain valve of pumps. 3.1. Stability of rubber modified bitumen during storage at high
This in turn can lead to serious damage and downtime in production, temperature – testing methods
and consequently economic losses. To prevent sedimentation of the
rubber granulate, it is necessary to continuously mix rubber modified To determine the stability of polymer-modified bitumen aging tests
bitumen [38]. Therefore, there is need to use tanks equipped with me- are performed in which in the beginning the aluminum tubes filled with
chanical stirrer. However, this is associated with the extra energy con- bitumen are vertically placed at the temperature of 180 °C for 72 h. Then
sumption and cost increase of production of paving with that kind of the tubes with bitumen are cooled down to ambient temperature and
bitumen. next to − 20 °C. After cooling, the aluminum coating is removed. The
samples in the form of cylinders are divided into three equal parts.
Upper and lower parts of cylinders are taken to determine the difference
3. Methods for improving storage stability of rubber modified in the penetration and in the softening point of these two parts of the
bitumen sample. Several studies serves only measurements of the difference in
softening temperature. In accordance with the requirements of EN
Polymers modified-bitumen are characterized by better 13399:2010 standard, bitumen is considered as stable when the differ-
physico-chemical properties compared to unmodified bitumen. ence between the values of the parameters tested for the upper and
Copolymer styrene-butadiene-styrene (SBS) and styrene-butadi- lower portion of the sample is not N9–26 units (dependently on catego-
ene rubber (SBR) are the most known polymers used to modify bi- ry of modified bitumen) in the case of penetration tests and no N5 units
tumen. But more and more often as a bitumen modifier is used in the case of the softening point test. The scheme of the stability deter-
ground tire rubber (GTR) obtained from spent tires, due to low mination of bitumen is shown in Fig. 1.
cost of GTR. These polymers affect the property improvements of Stability studies are sometimes performed under conditions other
bitumen such as fatigue resistance, rutting resistance, cracking at (Table 2) than those laid down in the standard described above which
low-temperature. However, a major problem is still low resistance makes it difficult to compare results from different laboratories.
to aging of polymer-modified bitumen, since in storage at high
temperature phase separation occurs leading to changes in proper- 3.2. Modifiers used to improve storage stability of rubber modified bitumen
ties (instability at high temperature) [37,47–48]. Comparing bitu-
men modified with SBS, SBR or GTR, it can be concluded that GTR- Currently, there are several known ways to improve the stability of
modified bitumen is the least stable. Although Table 1 shows that bitumen modified with crumb rubber from used tires. These methods
stability of bitumen modified with these polymers depends mainly are described in many patents and scientific articles [28–29,35,44–45,
on the amount of modifier. In addition, in the case of the SBS-mod- 60]. Navarro and co-workers showed, that the bitumen containing
ified bitumen, storage stability also depends on the structure of SBS 9 wt% of GTR with average grain size of about 0,29 mm is stable for
(linear or star-shaped) and may be improved by the addition of 12 h during storage at a temperature of 150 °C or 180 °C. While the bi-
sulfur or montmorillonite. In turn, the stability of SBR-modified bi- tumen modified with rubber granulate having average grain size of 0,35
tumen can be improved by sulfur with polyphosphoric acid or or 0,69 mm is not stable under these conditions. In this way they dem-
montmorillonite [27–28,37,47,49–53]. onstrated, that the stability of the rubber modified bitumen, is in accor-
In this chapter, characterized ways to improve the stability of dance with Stokes law and mainly depends on the grain size of GTR; the
rubberized bitumen described in the literature and used in the larger size of rubber granulates, the lower the stability [35].
industry. One way to improve the stability is use of various types Lo Presti [8] also showed that a stable rubberized bitumen can be ob-
of modifiers that form the bonds with components of these binders tained by using very fine rubber granulate (grains size below 0.3 mm),
e.g. sulfur [49] or trans-polyoctenamer rubber (TOR) [54]. The but the modification process must be carried out at very high tempera-
improvement of rubberized bitumen stability can also be obtained tures (200–300 °C) with a very high shear stress during the mixing of bi-
by means of complex polymer modifiers [55] e.g. compositions of tumen with rubber (mixing speed up to 8000 RPM) and optionally at a
high-density polyethylene (HDPE) [56] or low-density polyethyl- pressure higher than 1 atm. Under the influence of these conditions a
ene (LDPE) [57] with maleic anhydride-grafted ethylene-octene very fine rubber grains are devulcanized and “digested” in the bitumen
copolymer (POE-g-MA). The increase in stability can also be matrix (the solubility of rubber grains can reach more than 97%). For
achieved using crumb rubber surface-activated by furaldehyde this reason, the phase separation is not observed in the system. This sys-
(C5H4O2) [58] or acrylic acid [59]. tem is referred to as No-Agitation Recycled Tyre Rubber Modified

Table 1
The influence of modifier type on the storage stability of bitumen.

Type of Amount of Stability (softening point Comments References

modifier modifier [wt%] difference) [°C]

GTR 12.0 7.0 – [27]

6.0–26.0 0.9–13.4 – [28]
2.0–5.0 8.0–10.0 Stability was measured after storage at 140 °C. [49]
10.0–15.0 Stability was measured after storage at 160 °C.
2.0–8.0 Stability was measured after storage at 200 °C.
SBS 4.5 2.0 Stability may be improved by addition of antioxidants or UV absorbers to bitumen. [47]
3.5 14.0 Linear SBS was used. Differences in the softening point decrease to 0.2 °C when 0.1 wt% of [50]
sulfur is added to bitumen.
35.8 Star-shaped SBS was used. Differences in the softening point decrease to 0.1 °C when 0.1 wt%
of sulfur is added to bitumen.
5.0 5.2 Addition of montmorillonite improved stability of bitumen. [51]
SBR 2.0–6.0 2.1–6.4 Stability may be improved by addition of montmorillonite. [37]
2.9–5.7 2.0–17.0 Addition of sulfur and polyphosphoric acid improved stability of bitumen. [52]
4.0 0.2 – [53]
 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279 275

It is also interesting system patented, in which rubberized bitumen

are co-modificated by using peroxide and special compatibilizers. At
the start of modification process, the GTR is mixed with hydrogen per-
oxide at room temperature, and then heated to a temperature of 65–
75 °C. Hydrogen peroxide generates carbonium ions on the surface of
GTR grains. Farther, the bitumen is heated to a temperature of 160–
170 °C and mixed with a compatibilizer, which creates the bridges be-
tween bitumen and GTR grains. As a compatibilizer can be used methac-
rylate with glycidyl containing monomer, ethylene based glycidyl
containing monomer or a terpolymer of ethylene, butyl acrylate and
glycidal methacrylate. Bitumen surface modified in this way is much
smoother than conventional rubber modified bitumen, because GTR
does not form large clumps in the resulting system. This is due to the
better dispersion of GTR in bitumen when using special compatibilizers.
Fig. 1. The scheme of the bitumen stability estimation according to the requirements of EN Moreover, it was mentioned in the patent about improved rheological
13399:2010 standard. properties at low and high temperatures in the studied systems. How-
ever, not included details in this regard in the patent [68].
Bitumen (RTR-MBs) or terminal blended binder. There is no need to mix Biro and co-workers patented [69] a method of improving the stor-
the system during storage. Their production can be carried out using age stability of the rubber modified bitumen also by using several mod-
conventional equipment applied in the wet process of bitumen plant ifiers. First, bitumen was mixed with rubber granulate (3–40 wt%, grain
or asphalt mixture plant. Moreover, the modification process requires size below 2 mm) at the temperature of 70–230 °C. Then were intro-
no special asphalt mixers. Unfortunately RTR-MBs have worse final duced the modifiers A (hydrocarbons with oleophillic properties,
properties compared to the rubberized bitumen obtained in the stan- 0,03 wt%), B (polyolefins, 0,01–4 wt%) and C (amines, 0–2 wt%). After
dard wet process from rubber granulate with large particle size. This is adding all the components, the blend was stirred initially for 0.5–4 h,
because that the best efficiency of bitumen modification is achieved at the temperature of 200–270 °C, next for 0,5–6 h, at 190–160 °C. The
when the rubber grains are only partly swollen by the bitumen. Then obtained binder had constant softening point both before and after
only part of their cured structure is devulcanized. aging and it was stable during storage at high temperature. It was
There are several solutions to enhance the storage stability by adding claimed that it was due to adding the modifier A, forming bonds be-
some modifiers or compatibilizers for rubberized bitumen (Table 3). For tween bitumen molecules and rubber granulates.
example, the co-modification of bitumen by SBS copolymer and a small Perret et al. improved stability of rubber modified bitumen con-
amount of rubber granulate from waste tyres (approx. 6 wt%) allows to taining 7–13 wt% of rubber granulate with grain size between 0.01
obtain a relatively stable systems. That kind of solution has found the and 1 mm by using special kind of copolymer added to rubberized
application in Lotos Company (Poland), producing bitumen called bitumen in the amount of 1–2 wt%. The copolymer was prepared
MODBIT 45/80-55 CR. It is bitumen modified with SBS and crumb rub- by reaction of alphaolefin with unsaturated epoxides. Examples of
ber in the amount of 6 wt%. Based on studies of penetration and the soft- unsaturated epoxides may be chosen from: aliphatic glycidyl esters
ening point, it is concluded, that MODBIT 45/80–55 CR has good storage and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl
stability for 7 days at the temperature of 180 °C [62–64]. acrylate and methacrylate, and alicyclic glycidyl esters and
Ghaly showed good storage stability in the case of rubberized bitu- ethers such as 2-cyclohexene 1-glycidyl ether, diglycidyl 4,5
men modified with SBS and sulfur. It turned out that the top and bottom cyclohexenedicarboxylate, glycidyl 4-cyclohexenecarboxylate,
of the samples had the same softening points during storage up to 4 h at glycidyl 5-norbornene-2-methyl-2-carboxylate and diglycidyl
180 °C. These good properties were explained by the introduction of endocisbicyclo-5-heptene-2,3-dicarboxylate. In turn, as an alpha-
chemical bonds via sulfur between bitumen and granules of ground olefin may be used: ethylene, propylene, 1-butene, 1-hexene, 1-
tire rubber. Furthermore, the addition of sulfur had a positive impact decene. The authors concluded that the rubberized bitumen
on the penetration index, which can be explained by good stability of in- modified by the copolymer was stable after 3 days of storage at
troduced interactions with temperature changes [49]. 180 °C and it softening point was higher by about 13–20 °C while
Also known are studies [54,65–67] that describe using 4% of trans- penetration value decreased by 15–30 [1/10 mm] compared to
polyoctenamer rubber (TOR) in the modification of storage stability of non-modified rubberized bitumen [70].
rubberized bitumen. TOR, having unsaturated bonds may react with sul- Shatanawi et al. have shown method of improving stability of
fur from asphaltenes as well as sulfur present on the surface of ground rubberized bitumen by using GTR (7,4 wt%) activated with the use
rubber, to form a network structure of polymer chains. In addition, rub- of 2-furaldehyde (C5H4O2). Thus modified GTR has higher reactivi-
berized bitumen with TOR has a lower decrease in viscosity after storage ty, which results in greater interactions between the GTR and bitu-
for 24 h at a temperature of 177–190 °C in comparison with rubberized men. Furthermore, it was noted that the bitumen modified by GTR
bitumen without TOR under the same conditions that is positive effect obtained from tyres grinded at ambient temperature was more sta-
on improving the workability of rubberized bitumen [54]. ble than bitumen modified by GTR obtained by cryogenical process.
It was explained by higher specific surface area of GTR processed
Table 2 cryogenically [58].
Conditions of the storage stability tests performed in some laboratories. The Noweko [71] offers modifier (CGA 180) of bitumen containing
Test method Conditions of storage the samples References activated rubber powder (AGP), surrounded by thermoplastic material
as adhesive promoters and additive reducing viscosity. CGA 180 is pro-
Period of time [h] Temperature [°C]
duced as granules with grain size of about 4 mm. Bitumen modified by
A 72 180 EN 13399:2010
CGA 180 has improved stability at high temperature due to presence of
B 12 150–180 [35]
C 24 177–190 [54] thermoplastic parts, which after melting float particles of GTR in bitu-
D 48 140–200 [49] men. In this way, particles of GTR are uniformly distributed in total
E 48 163 [57,61] weight of bitumen and cannot settle. Moreover it was found that CGA-
F 120 163 [27] modified bitumen had very good processing and improved properties
G 240 180 [62–64]
during the contact of tire with road.
276 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279

Table 3
The influence of type of modifiers/compatibilizers on the storage stability of rubberized bitumen obtained from ground tire rubber.

Modifiers/compatibilizers of Comments Result References

rubberized bitumen

SBS (copolymer SBS added as a partial replacement of GTR. Bitumen containing 6 wt% of GTR is stable for [62–64]
styrene-butadiene-styrene) Lack of chemical interactions between SBS, GTR and bitumen. 7 days at 180 °C.
SBS/sulfur Formation of chemical bonds between bitumen and GTR via sulfur. Sulfur addition improves the storage stability of [49]
bitumen.
TOR (trans-polyoctenamer rubber) Unsaturated bonds present in TOR react with sulfur from Addition of TOR improves stability of bitumen [54]
asphaltenes and with sulfur present on the GTR surface, creating during storage.
network structure of polymer chains.
Hydrogen peroxide/compatibilizer Hydrogen peroxide was used to generate carbonium ions on the Homogenous binder is obtained due to the better [68]
surface of GTR grains. dispersion of GTR in bitumen as a result of
Compatibilizer creates the bridges between bitumen and GTR compatibilizer use.
grains.
As a compatibilizer may be used methacrylate with glycidyl
containing monomer, ethylene based glycidyl containing monomer
or a terpolymer of ethylene, butyl acrylate and glycidal
methacrylate.
A (Hydrocarbons with oleophillic Modifier A forms bonds between bitumen molecules and GTR. Stable bitumen with improved properties is [69]
properties)/B (polyolefins)/C Modifier B was used to decrease the viscosity of bitumen. obtained.
(amines) Modifier C was used as anticorrosion and/or antioxidant additives.
Copolymer Copolymer was prepared by reaction of alphaolefin with Rubberized bitumen modified by copolymer is [70]
unsaturated epoxide. stable after 3 days storage at 180 °C.
Examples of used alpha-olefins: ethylene, propylene, 1-butene,
1-hexene, 1-decene.
Examples of used unsaturated epoxides: aliphatic glycidyl esters
and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl
acrylate and methacrylate.
C5H4O2 (2-furaldehyde) C5H4O2 was used as an activator of GTR before its addition to Activated GTR results in greater interactions [58]
bitumen. between GTR and bitumen thus improved stability
of rubberized bitumen is achieved.
CGA 180 CGA 180 was obtained with activated rubber powder (AGP), Particles of GTR are uniformly dispersed due to [71]
surrounded by thermoplastic material, adhesive promoters and presence of thermoplastic parts, which after
additives reducing viscosity. melting floats particles of GTR in bitumen.
LDPE/POE-g-MA (low density Compositions of GTR, HDPE or LDPE and POE-g-MA were added to Improved the storage stability of bitumen modified [56–57]
polyethylene/maleic bitumen instead of GTR part due to their lower density than GTR. by such compositions in comparison with bitumen
anhydride-grafted ethylene-octene POE-g-MA acts as a compatibilizer between GTR, bitumen and LDPE modified only by GTR.
copolymer) or HDPE.
HDPE/POE-g-MA (high density
polyethylene/maleic
anhydride-grafted ethylene-octene
copolymer)
Inorganic acid Inorganic acid may be chosen from: sulfuric acid, phosphoric acid, Stability of bitumen may be improved only if [72]
hydrochloric acid and mixture. inorganic acid is added before GTR or other
GTR present in bitumen may be replaced by thermosets or polymer.
thermoplastics
TecRoad TecRoad was obtained in a form of granulated bitumen containing TecRoad is stabile additive of bitumen. [81–85]
GTR, oils, silica and fillers. Addition of TecRoad improves properties of asphalt
TecRoad is used as an additive to asphalt concrete. concrete.
Additives Additives:compatibilizers, modifiers, plasticizers Improved stability in comparison with bitumen [76]
Bitumen, GTR and additives mixed using twin screw extruder. obtained by traditional wet method.

As has been already mentioned [10,35,38], one of the reasons that having a high storage stability at high temperature. According to the in-
rubber modified bitumen exhibits instability is the density difference vention, to the hot (163–288 °C), rapidly stirred bitumen, crumb rubber
between the bitumen and the GTR. Wang and co-workers [56] and (0,5–25 wt%) was added and polyphosphoric acid (0,05–5 wt%). The
Ouyang and co-workers [57] prepared bitumen modified by polymeric modification process was carried out for 1–24 h and this time, includes
compositions with lower density than GTR. Low density polyethylene also the step of blowing air through the system thus obtained [73–75].
(LDPE) and maleic anhydride-grafted ethylene-octene copolymer Formela and Maslanka patented a method improving stability of
(POE-g-MA) with GTR compositions was analyzed by Oyuang and co- rubber modified bitumen by using twin screw extruder (the tempera-
workers. While Wang and co-workers obtained composition containing ture of cylinder 60–400 °C). The compositions contained bitumen 160/
GTR, HDPE (high density polyethylene) and POE-g-MA. Both teams 220 (max. 99 wt%), ground rubber (1–99 wt%; grain
found that studied compositions were more stable at high temperature diameter b 5 mm), and additives (compatibilizer, modifiers, plasticizers,
in comparison to bitumen modified only by GTR and POE-g-MA ap- max. 80 wt%). According to the authors, the obtained binders are char-
peared as good compatibilizer of bitumen and GTR. acterized by better stability in comparison to binders obtained by tradi-
Rubber modified bitumen with an improved stability at high tem- tional method [76].
peratures during storage may also be obtained by treating bitumen It is also possible to modify asphalt concrete with compositions
with inorganic acid, but in the case of polymer-modified composition containing GTR partially swellen by the bitumen and additives
this step should be carried out prior to polymer introduction It was re- (polymers, compatibilizers, oils, fillers and adhesive promoters).
ported that inorganic acid may be chosen from sulfuric acid, phosphoric These compositions, commercially known as RuBind or TecRoad
acid, hydrochloric acid or mixture of thereof [72]. improve cost effectiveness and properties of rubber-asphalt
Martin patented a method of modifying bitumen with waste rubber, concrete in comparison with rubberized bitumen obtained in wet
and polyphosphoric acid, which allows to obtain rubberized bitumen process.
 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279 277

RuBind consists of GTR, bitumen and activated mineral binder stabi- of them are currently used in the industry, which is a performance cer-
lizer (AMBS). AMBS is an activated silica mineral, that interacts electro- tificate of their effectiveness.
statically with the components of rubber granulate. In addition to good Based on the information collected and presented in this review ar-
stability, asphalt concrete containing RuBind has good resistance to rut- ticle the following conclusions may be drawn:
ting and fatigue strength [77–80].
The Rubbertec Company produces „tecRoad”, which characterizes • A significant improvement in the stability of the rubber-modified bi-
by good stability at high temperature. It is granulated bitumen modified tumen may be a consequence of the use rubber granulates with a
by 30–40 wt% of GTR, suitable fillers (not mentioned in company mate- small grain size, b 0.3 mm and with a well-developed specific surface
rials data), oils, silica and mineral aggregates. Moreover, the addition of area. From this point of view, ground rubber obtained under ambient
tecRoad to asphalt concrete leads to increased strength, improved resis- conditions is much better modifier than that achieved in a cryogenic
tance to rutting and low-temperature cracking as compared to unmod- process. Moreover, it was found that use of very fine crumb rubber
ified asphalt, even with a low amount of tecRoad (2 wt%). Therefore, it is in the process of bitumen modification may even cause their
used especially for road surfaces with high traffic loads. Furthermore, devulcanization and “digestion” in bitumen matrix. The improvement
due to the filler used to produce tecRoad, it does not require additional in the stability of rubberized bitumen might be also achieved when in
stabilizers or modifiers [81–85]. the modification process is used devulcanized rubber (obtained in
Improvement of the storage stability of rubber modified bitumen thermo-mechanical, physical or chemical devulcanization process).
can also be achieved by the appropriate treatment of GTR before it is Unfortunately, this modification results in a reduction of the global
added to bitumen (Table 4). Based on the results shown in Table 4 fol- properties of rubberized bitumen, because the best modification effi-
lowing proposals to improve storage stability can be formulated: ciency is achieved when the rubber grains are merely swollen by the
bitumen and their cured structure is only partially devulcanized.
• Storage stability of bitumen modified by GTR can be improved by dy- • The best way to improve the stability of rubber modified bitumen can
namic vulcanization of GTR with thermoplast (LLDPE) [86]. be achieved when to rubberized bitumen are added the chemical
• Adding desulfurized GTR better improves the storage stability of mod- compounds that have the ability to physical and chemical interactions
ified bitumen than untreated GTR [87]. between the particle of rubber and bitumen. Such compounds may in-
• GTR activated by gamma radiation is one solution aimed at improving clude trans-polyoctenamer rubber (TOR), mixture of sulfur and SBS
the storage stability of rubberized bitumen [88]. copolymer, peroxides and acrylate-glycidyl copolymers, compositions
of high-density polyethylene (HDPE) or low-density polyethylene
(LDPE) with maleic anhydride-grafted ethylene-octene copolymer
4. Conclusions (POE-g-MA). The significant increase in stability can also be obtained
by the use of crumb rubber in which the surface was activated by
The use of crumb rubber from waste tires for asphalt modification furaldehyde or acrylic acid.
provides many benefits, not only in the field of management of the • Rubber modified bitumen with improved stability at high tempera-
growing amount of waste tires, but also because of the favorable im- ture may also be obtained by using available on the market of com-
provement of physical and mechanical properties of the asphalt, leading mercial rubber modifiers of bitumen such as RuBind (SHRP
to an increase in the durability of asphalt roads. CORPORATION) and tecRoad (Rubbertec). These modifiers are a mix-
The disadvantage of the use of ground tire rubber as a bitumen ture of crumb rubber (30–40 wt%) partially swellen with bitumen,
modifier (in wet process) is the instability of rubber modified bitu- polymers, oils, adhesion promoters and compatibilizers. According
men during storage at high temperature (approx. 180 °C). This is a to the manufacturers recommendations modifiers should be added
serious problem that limits the industrial use of modified bitumi- into the bitumen prior to mixing them with mineral aggregates.
nous materials. • Thus, the procedure of the bitumen modification with these com-
However, as shown herein, recently there are numerous ways of im- pounds is similar to the dry process, but the properties of rubberized
proving the storage stability of the rubber-modified bitumen, and some bitumen and cost modification is improved and comparable to the

Table 4
The influence of component type, particle size of rubber granulate, components ratio and processing on the storage stability of rubber modified bitumen obtained from ground tire rubber.

Components of Components Average Preparation of rubber Comments Results References

rubberized mass ratio particle modified bitumen
bitumen [wt%] size of
GTR [mm]

Bitumen 88,5 0.595 Mixing with high-shear TPEs were previously dynamic devulcanized (DD) DV process improved storage [86]
TPEs 11,5 mixer at 180 °C for using twin-screw extruder and dynamic stability of TPEs modified bitumen.
30 min. vulcanized (DV) with sulfur vulcanization system,
then added to bitumen;
TPEs was obtained from GTR and LLDPE with
components ratio 7:3 respectively;
Waste truck rubber was used.
Bitumen 80 0.4 Blending for 1 h at 180– Desulfurized ground tire rubber was obtained Desulfurized GTR modified bitumen [87]
dGTR 20 190 °C then cultivated for with special desulfurization process combined have better storage stability than
(desulfurized 30 min. at the same with chemically plasticizing and activating bitumen modified by untreated GTR.
ground tire temperature treatments; Higher differences of value between
rubber) Storage stability tests were performed at different upper and lower part of binder
storage time and at different storage temperature; increase with storage time and
temperature increases.
Bitumen 90–95 2 Mixing with high-speed GTR was activated by gamma irradiated at 100, The higher irradiated of GTR the [88]
GTR 5–10 shearing and dispersing 200 and 300 kGy. better storage stability of rubberized
emulsifying machine at bitumen.
170 °C for 1 h
278 M. Sienkiewicz et al. / Fuel Processing Technology 159 (2017) 272–279

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