Construction and Building Materials 186 (2018) 863–870

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Construction and Building Materials

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

Halogen-free flame retarded cold-mix epoxy asphalt binders:

Rheological, thermal and mechanical characterization
Ru Chen a, Jie Gong a, Yongjia Jiang a, Qingjun Wang a, Zhonghua Xi b, Hongfeng Xie a,⇑
a
Key Laboratory of High Performance Polymer Materials and Technology of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
b
Experimental Chemistry Teaching Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

h i g h l i g h t s

Halogen-free flame retarded cold-mix epoxy asphalt binder (CEAB) has been developed.

The flame retardancy of the neat CEAB is significantly increased by halogen-free flame retardant.

The addition of halogen-free flame retardants improves the glass transition temperature, thermal stability and tensile strength of the neat CEAB.

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

Article history: Fire safety of asphalt mixtures in highway tunnels has become a problem of great concerns since asphalt
Received 22 June 2018 and polymer modified asphalt binders are quite flammable and tend to release poisonous gases and
Received in revised form 4 August 2018 smoke while burning. Therefore, flame retardants are incorporated into asphalt binder to improve the fire
Accepted 4 August 2018
retardancy of asphalt mixtures. In this paper, aluminum trihydroxide (ATH) and zinc borate (ZB) were
Available online 10 August 2018
used as halogen-free flame retardants to prepare flame retarded cold-mix epoxy asphalt binders
(CEABs). The addition of halogen-free flame retardants increased flame retardancy of the neat CEAB. In
Keywords:
addition, ATH-ZB retarded CEAB had higher limited oxygen index (LOI) than single ATH and ZB retarded
Epoxy asphalt
Aluminum trihydroxide (ATH)
CEABs at the same content. The presence of halogen-free flame retardants increased the viscosity of the
Zinc borate (ZB) neat CEAB. The viscosity of ATH/ZB retarded CEAB was lower than that of ATH retarded CEAB at a specific
Flame retardant content. The incorporation of halogen-free flame retardants enhanced the glass transition temperature of
Halogen-free flame retardant the neat CEAB. Thermal stability of the neat CEAB was improved by the halogen-free flame retardants.
Glass transition temperature ATH/ZB retarded CEAB had better thermal stability than ATH retarded CEAB at the same content. The
Thermal stability addition of halogen-free flame retardants increased the tensile strength of the neat CEAB. Uniform
Mechanical properties dispersion of halogen-free flame retardants in CEABs was observed.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction tunnels due to their excellent surface evenness, skid resistance

Rigid pavements of Portland cement concrete (PCC) and flexible
pavements of asphalt mixtures are currently known and used road
pavements for tunnels [1]. It is well accepted that PCC has a higher
fire resistance and thermal stability and very low emission of toxic
gases, which assures the evacuation of people and the transit of
vehicles in the event of fire. However, PCC pavements contain dif-
ficulties and defects in paving and maintenance, resulting in inad-
equate performances with regards to functional characteristics. In
addition, compared to the asphalt mixtures, the costs of PCC pave-
ments for construction and subsequent maintenance are much
higher. Thus, asphalt mixtures have been widespreadly used in
⇑ Corresponding author.
E-mail address: hfxie@nju.edu.cn (H. Xie).
and ease of application. However, as a mixture of hydrocarbons,
asphalt is flammable. When used in tunnel construction, asphalt
can be ignited at less than 300 °C and release toxic smoke and heat.
Thus, the development of flame retarded asphalt binders with add-
ing organic and inorganic flame retardants (FRs) has become a
preferable solution to improve the fire retardancy of flexible pave-
ments in tunnels [2–4]. Among all organic FRs, brominated flame
retardants (BFRs) have been widely used in asphalt mixtures
[5,6]. Due to concerns about the persistence, bioaccumulation,
and toxicity (PBT), some BFRs, such as brominated diphenylethers
(BDEs) and polybrominated biphenyls (PBBs) halogenated flame
retardants have been banned to use in the last decade [7]. Hence,
the use and demand of halogen-free flame retardants to substitute
BFRs have grown rapidly [8]. As the main halogen-free flame retar-
dants, mineral fillers, especially aluminum trihydrate (ATH) and

https://doi.org/10.1016/j.conbuildmat.2018.08.018
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
864 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870

magnesium hydroxide (MH), have attracted increasingly interest
for asphalt binders [9–12].
Epoxy asphalt (EA) is a thermosetting polymer modified
asphalt, which is mainly made up of epoxy monomer, curing agent
and asphalt [13–15]. Epoxy asphalt binder can be classified into
three types according to mixing temperature: hot-mix epoxy
Mechanical properties of the neat CEAB and flame retarded CEABs were per-
formed by an Instron 3366 universal test machine (Norwood, MA, USA) according
to ASTM D638. At least five samples were measured with a strain rate of
200 mm/min.
The morphology of the neat CEAB and flame retarded CEABs was observed by a
field-emission scanning electron microscopy (FE-SEM). The sample was surface
fractured in the liquid nitrogen and coated with gold before SEM observations.

asphalt binder (HEAB, 160–190 °C), warm-mix epoxy asphalt bin-

der (WEAB, 110–140 °C) and cold-mix epoxy asphalt binder (CEAB, 3. Results and discussion
ambient temperature) [16–18]. When epoxy monomer and curing
agent are mixed together, an irreversible cure reaction will take 3.1. Flammability
place and form three dimensional crosslinking networks, in which
asphalt molecules are restricted [19–22]. As a result, thermoplastic LOIs of the neat CEAB and flame retarded CEABs are presented
asphalt turns to thermosetting elastomer, endowing epoxy asphalt in Fig. 1. The LOI of the neat CEAB is 20.0%, indicating that CEAB
mixtures with high strength and toughness, good fatigue resis- is very flammable. Obviously, the addition of flame retardants
tance, skid resistance and temperature stability and long durability increases the LOI of the neat CEAB. Additionally, the LOI of ATH
[23,24]. Epoxy asphalt binder has been widely used not only on the and ZB retarded CEABs increases with the increase of flame retar-
steel bridge decks, especially in China, but also in tunnels, on air- dant contents. At a specific content, the LOI of ZB retarded CEAB is
fields and porous asphalt pavements with high durability and at slightly higher than that of ATH retarded CEAB. However, the LOIs
intersections of heavy duty roads [25,26]. However, epoxy asphalt of both ATH and ZB retarded CEABs are lower than that of ATH/ZB
is also quite combustible and produces much smoke and toxic retarded one at the same content. This indicates ZB has synergistic
gases since both asphalt and epoxy resin is intrinsically flammable effect on the flame retardancy of ATH in the neat CEAB. Similar
[27]. It will be hazard to pave non-flame-retarded epoxy asphalt results were also reported in ATH/ZB modified rigid poly
mixtures in tunnels. Consequently, to improve the fire resistance (vinyl chloride) (PVC) [28]. For ATH/ZB retarded CEABs, LOIs of
of epoxy asphalt binder is of great importance. all ATH/ZB modified CEABs are greater than 23%. CEAB with
In present paper, ATH and ATH combined with zinc borate (ZB)
were used as halogen-free flame retardants to improve the flame
retardancy of cold-mix epoxy asphalt binder. Oxygen index instru-
ment, Brookfield rotational viscometer, differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), tensile test
and scanning electron microscopy were employed to determine
the influence of halogen-free flame retardants on the flame retar-
dancy, viscosity, glass transition temperature (Tg), thermal stabil-
ity, mechanical properties and morphology of cold-mix epoxy
asphalt binders.

2. Experimental

2.1. Materials

Cold-mix epoxy asphalt binder contains two components: epoxy monomer and
asphalt with curing agent. Epoxy monomer is diglycidyl ether of bisphenol A
(DGEBA). An amine cure agent (NDB196B) was prepared by our laboratory. ATH
is white powder with Al(OH)3 content more than 99.4%. Its average particle size
is 1250 mesh. Zinc borate (2ZnO∙3B2O33.5H2O) was also white powder with aver-
age particle size of less than 7 lm. The weight ratio of ATH/ZB is 3:1.
Fig. 1. LOIs of the neat CEAB, CEAB/ATH, CEAB/ZB and CEAB/ATH/ZB composites.

2.2. Samples preparation

DGEBA and NDB196B were heated at 60 °C and mixed a 250 mL beaker at

2000 rpm for 5 min. Then, ATH, ZB or ATH/ZB was introduced into the CEAB mixture
and agitated using Fluko FM300 high-shear emulsifier (Shanghai, China) at
3000 rpm at 5 min. Finally, the mixture was cured for 2 days at 60 °C in Toflon
molds. The weight percents of ATH, ZB or ATH/ZB in CEABs were 10, 20 and 30,
respectively.

2.3. Tests and measurements

Limited oxygen index (LOI) of flame retarded CEABs were tested with HC-2C
oxygen index instrument (China) on the sheets of 100 mm  10 mm  4 mm
according to ASTM D2863.
Rotational viscosities of the neat CEAB and flame retarded CEABs were mea-
sured in a Brookfield rotational viscometer with spindle 28 (NDJ-1C, China) under
the guideline of ASTM D4402. The rotational viscosity began to be recorded when
all components of samples were stirred at 3000 rpm at 5 min.
The Tgs of the neat CEAB and flame retarded CEABs were evaluated by differen-
tial scanning calorimetry (DSC) (Mettler Toledo DSC 1, Leicester, UK). The DSC mea-
surements were carried out from 20 to 80 °C at a ramp rate of 20 °C/min under a
nitrogen purge.
Thermal stabilities of the neat CEAB and flame retarded CEABs were determined
by a Mettler Toledo TGA/DSC 1 Stare system (Leicester, UK). The test was performed Fig. 2. Viscosity versus time curves of the neat CEAB and flame retarded CEABs at
from 50 to 600 °C with a heating rate of 20 °C/min under a nitrogen purge. 60 °C.
 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870 865

20 wt% ATH/ZB has a maximum LOI value (23.7%). According to
GB/T 29051-2012 [29], the LOI of asphalt binder used in tunnel
needs to be greater than 23%. Obvious, only ATH/ZB retarded
CEABs can meet this LOI standard.
It is known that ATH decomposes in Al2O3 as well as strongly
endothermic reactions during the heating to the flame-retarded
polymeric material, which lead to an increment of ignition time.
The mode of combined action of ZB and ATH is summed up as fol-
lows [30]:
boric oxide can serve as a sintering aid for alumina. The decompo-
sition of ZB can release 13.5% of water with an endothermicity of
503 J/g at high temperature. The release of crystallization water
molecules reduces the temperature of polymer surface and dilutes
organic volatiles and the concentration of H radicals in the flame.
Thus, the existence of ZB forms more chars and releases more
water to more effectively suppress combustion [31]. This synergis-
tic effect of ZB on the flame retardancy of metal hydroxides was
also reported by other researchers [32].

2ZnO  3B2 O3  3:5H2 O þ AlðOHÞ3 ! xAl2 O3  yZnO  Zb2 O3 3.2. Viscosity

þ B2 O3 þ H2 O "
A porous and ceramic-like char of boric oxide and alumina
formed at temperatures above 600 °C acts as an insulator layer
for the underlying unburned polymeric material. In addition, the
Table 1
Time to 3000 mPa∙s for the neat CEAB and flame retarded CEABs.
Unlike traditional asphalt binders, epoxy asphalt binder is a
reactive polymer blend. During cure reaction, molecular weight
of epoxy increases, inevitably resulting in the increase of the vis-
cosity [33]. Thus, the viscosity of CEAB should be well controlled
to leave enough time for mixtures’ mixing, transporting and pav-
ing. Fig. 2 depicts the viscosity-time curves of the neat CEAB and

Flame retardant (wt%) Time to 3000 mPa∙s (min) Table 2

Tgs of CEAB/ATH and CEAB/ATH/ZB composites.
ATH ATH/ZB
0 114 114 Flame retardant (wt%) Tg (°C)
10 93 108 ATH ATH/ZB
20 88 102
0 25.5 25.5
30 74 88
10 25.9 26.0
20 26.2 27.5
30 27.3 28.1

Fig. 3. DSC curves of the neat CEAB, CEAB/ATH (a) and CEAB/ATH/ZB (b)
composites. Fig. 4. TGA (a) and DTG (b) curves of ATH, ATH/ZB and ZB.
866 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870

flame retarded CEABs at 60 °C. Evidently, the addition of flame in Table 2. The addition of flame retardants increases the Tg of the
retardants increases the viscosity of the neat CEAB during the neat CEAB (25.5 °C). In addition, Tg of flame retarded CEABs
whole curing process. Besides, the viscosity of CEAB/ATH/ZB com- increases with the increase of flame retardant contents. The Tg of
posites is much lower than that of CEAB/ATH composites during ATH/ZB retarded CEABs is slightly higher than that of ATH retarded
the cure reaction, indicating the existence of ZB more effectively CEABs at a specific content. The effect of particle incorporation on
hinders the cure reaction of the neat CEAB. the Tg of polymeric materials depends on the dispersion of parti-
According to the technical requirements of Strategic Highway cles in the matrix and the interaction between particles and poly-
Research Program (SHRP), the viscosity of asphalt binder for mix- mer [35–37]. Ma et al. reported that the interfacial interaction
ture pavement should be lower than 3000 mPa∙s [34]. Table 1 sum- between ATH and epoxy is physical interaction. ATH inherent
marizes the time to 3000 mPa∙s for the neat CEAB and flame aggregates result in the decrease of epoxy’s Tg [38]. The dispersion
retarded CEABs. Obviously, the addition of flame retardants short- of flame retardants in the CEAB matrix will be discussed in the
ens the time to reach the SHRP specification. Compared to ATH ‘‘morphology” section.
retarded CEAB, ZB/ATH retarded CEAB has longer time to satisfy
the SHRP technical requirement. This indicates that the presence 3.4. Thermal stability
of ZB increases the construction time for ATH retarded CEABs.
Fig. 4 shows TGA and derivative thermogravimetric (DTG)
3.3. Glass transition temperature curves of flame retardants. Thermal parameters of flame retardants
are summarized in Table 3. The one-stage thermal degradation of
Fig. 3 presents DSC curves of the neat CEAB and ATH and ATH/ ATH occurs between 220 and 320 °C with a temperature at the
ZB retarded CEABs. Tgs obtained from DSC curves are summarized maximum degradation rate (Tmax) of 291.0 °C and an initial degra-
dation temperature (IDT, the temperature at 5% thermal pyrolysis)
Table 3 of 267.7 °C. The char at 600 °C of 66.2% corresponds to the dehy-
Thermal parameters of flame retardants. dration of ATH, resulting in the formation of alumina (Al2O3). The
Flame retardant IDT (°C) T1max (°C) T2max (°C) Char at 600 °C (%) thermal degradation of ZB undergoes in two steps. The first step
occurs between 275 and 345 °C corresponding to a weight loss of
ATH 267.7 291.0 – 66.2
ATH/ZB 268.6 285.6 427.2 69.7 about 2%. The second step takes place between 345 and 470 °C
ZB 393.4 320.1 426.5 86.7 with a weight loss of about 13%, attributing to loss of water. The
IDT of ZB is 393.4 °C, which is much higher than that of ATH.

Fig. 5. TGA (a) and DTG (b) curves of the neat CEAB and CEAB/ATH composites. Fig. 6. TGA (a) and DTG (b) curves of the neat CEAB and CEAB/ATH/ZB composites.
 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870 867

Due to the combined effect of two flame retardants, the thermal the first step becomes more evidently with the increase of flame
degradation of ATH/ZB also occurs in two stages. In addition, the retardant contents.
IDT and char at 600 °C of ATH/ZB are higher than those of ATH. Table 4 summarizes thermal parameters of the neat CEAB, ATH
Figs. 5 and 6 depict TGA and DTG curves of the neat CEAB, CEAB/ ant ATH/ZB retarded CEABs. Evidently, the addition of flame retar-
ATH and CEAB/ATH/ZB composites. The thermal degradation of the dants elevates the values of IDT, Tmax and char at 600 °C of the neat
neat CEAB composes of two steps. First, weaker chemical bonds of CEAB. In addition, thermal parameters of flame retarded CEABs
asphalt and unreacted epoxy are broken from 200 to 350 °C. Sec- increase with the increase of flame retardant contents. At a specific
ond, larger molecules of asphalts degrade into smaller molecules content, ATH/ZB retarded CEAB has higher thermal parameters
and epoxy crosslinking networks decompose from 350 to 500 °C than ATH retarded CEAB, attributing to the higher thermal stability
[39]. The thermal degradation of ATH and ATH/ZB retarded CEABs of ZB. Taking account of the effect of filler content, the values of the
also undergoes two steps. Moreover, as shown in Figs. 5b and 6b, char at 600 °C subtracting the filler content, that is, chars referred
only to the binder in the flame-retarded CEABs are also listed in
Table 4. For ATH modified CEABs, the char at 600 °C of the binder
decreases with increasing filler contents. However, in terms of
Table 4 ATH/ZB modified CEABs, a maximum value of char at 600 °C of
Thermal parameters of the neat CEAB, ATH ant ATH/ZB retarded CEABs.
the binder reaches at 20 wt% filler content. At a specific content,
Content IDT T1max T2max Char at Char at 600 °C the char at 600 °C of the binder for ATH/ZB modified CEABs is
(wt%) (°C) (°C) (°C) 600 °C subtracting the higher than that of ATH modified CEABs. As discussed previously,
(%) filler content (%)
the porous and ceramic-like char of boric oxide and alumina
0 247.9 328.2 379.6 7.9 7.9 formed by ATH and ZB at temperatures above 600 °C acts as an
ATH 10 261.3 330.7 383.3 14.7 8.1 insulator layer for the underlying unburned polymeric material.
20 264.1 337.7 385.3 17.9 4.7
30 265.8 338.3 389.5 20.8 1.0
The more chars formed by ATH/ZB, the better flame retardancy
ATH/ZB 10 266.7 341.0 383.8 17.8 10.8 of polymeric material. Accordingly, it is not surprised to find that
20 267.7 340.3 385.6 21.0 14.0 the CEAB with 20 wt% ATH/ZB exhibits the best flame retardancy
30 269.0 343.8 390.5 25.6 4.6 among all the flame-retarded CEABs. Therefore, it can be concluded
that the addition of ATH and ATH/ZB enhances the thermal stabil-
ity of the neat CEAB. Additionally, the addition of ZB synergistically

Fig. 7. Tensile strength (a) and elongation at break (b) of the neat CEAB, CEAB/ATH Fig. 8. Toughness (a) and Young’s modulus (b) of the neat CEAB, CEAB/ATH and
and CEAB/ATH/ZB composites. CEAB/ATH/ZB composites.
868 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870
retards the thermal degradation of both the neat and ATH retarded
matrix system, resulting in the enhancement of the flame retar-
dancy of the system at lower filler loading.
3.5. Mechanical properties
Fig. 7 presents the tensile strength and elongation at break of
the neat CEAB and flame retarded CEABs. The addition of flame
retardants increases the tensile strength of the neat CEAB. This
can be attributed to stress transfer from filler to polymer. Opposite
results were reported in ATH/ZB retarded polypropylene (PP) sys-
tems [40]. The tensile strength of flame retarded CEABs increases
with the increase of flame retardant contents. Except for 30 wt%
loading, the tensile strength of ATH retarded CEAB is greater than
that of ATH/ZB retarded CEAB at a specific content. The addition
of flame retardants decreases the elongation at break of the neat
CEAB. Similar results were also observed in ATH/ZB modified PVC
systems [41]. For ATH retarded CEABs, the elongation at break
decreases with the increase of ATH contents. For ATH/ZB retarded
CEABs, however, the elongation at break reaches a maximum value
at 20 wt% loading and then decreases greatly with the increase of
flame retardant contents. According to the technical requirement
of CEAB, the tensile strength and elongation at break need to be
greater than 2.0 MPa and 80%, respectively. Unquestionably, all
tensile strengths of flame retarded CEABs satisfy this requirement.
Fig. 9. SEM micrographs of the neat CEAB (a) and flame retarded CEAB composites: 10 wt% ATH (b); 20 wt% ATH (c); 30 wt% ATH (d); 10 wt% ATH/ZB (e); 20 wt% ATH/ZB (f);
30 wt% ATH/ZB (g).
However, elongations at break CEABs with 30 wt% flame retardants
are lower than the value required by the technical specification.
Generally, the area under the stress–strain curve has been used
to evaluate the toughness (the value of energy consumed for frac-
turing the material) [42]. Fig. 8 shows toughness and Young’s mod-
ulus of the neat CEAB and flame retarded CEABs. The addition of
flame retardants lowers the toughness of the neat CEAB. For ATH
retarded CEABs, the toughness decreases with the increase of
ATH contents. However, for ATH/ZB retarded CEABs, a maximum
toughness comes out at the content of 20 wt%. At a specific con-
tent, the toughness value of ATH retarded CEAB is greater than that
of ATH/ZB retarded CEAB. As shown in Fig. 8b, the addition of flame
retardants also reduces the Young’s modulus of the neat CEAB. The
flame retardant content has little effect on the Young’s modulus of
flame retarded CEABs. The Young’s modulus of ATH retarded CEAB
is lower than that of ATH/ZB retarded CEAB at a specific content.
3.6. Morphology
Fig. 9 presents SEM images of the neat CEAB and flame retarded
CEABs. The neat CEAB exhibits a smooth surface. As shown in
Fig. 9b–d, good dispersion of ATH in the CEABs is observed. In addi-
tion, the ratio of rough fracture surface increase with the increase
of ATH contents. As shown in Fig. 9e–g, the dispersion of ATH/ZB in
the CEAB matrix is not as good as that of ATH. Fewer rough fracture
 R. Chen et al. / Construction and Building Materials 186 (2018) 863–870
surfaces are observed as compared to ATH retarded CEABs. These
SEM observations support the increment of Tg and tensile strength
as discussed above.
4. Conclusions
Two kinds of halogen-free flame retardants, ATH and ATH/ZB
were incorporated into CEABs to prepare flame retarded CEABs.
The flame retardancy of CEABs increases with the increase of flame
retardant contents. ATH/ZB retarded CEAB has higher LOI than sin-
gle ATH and ZB retarded CEABs at a specific content. The addition
of halogen-free flame retardants increases the viscosity of the neat
CEAB. The viscosity of ATH retarded CEAB is higher than that of
ATH/ZB retarded CEAB at a specific content. ZB/ATH retarded CEAB
has longer time to satisfy the SHRP technical requirement. The
addition of halogen-free flame retardants increases the Tg of the
neat CEAB. Tg of ATH/ZB retarded CEAB is slightly higher than that
of ATH retarded CEAB at the same content. The presence of
halogen-free flame retardants improves the thermal stability of
the neat CEAB, especially for ATH/ZB. The inclusion of halogen-
free flame retardants enhances the tensile strength of the neat
CEAB. ATH retarded CEAB has higher tensile strength than ATH/
ZB retarded CEAB at the same content. The incorporation of
halogen-free flame retardants lowers the elongation at break,
toughness and Young’s modulus of the neat CEAB. Better disper-
sion of ATH in the CEAB matrix is observed as compared to ATH/
ZB. Compared with single ATH, ATH/ZB retarded CEABs exhibit
higher flame retardancy, Tg and thermal stability.
Declaration of conflicting interest
The authors declare no conflict of interest.
Acknowledgements
The financial support from Changjiang Scholars and Innovative
Research Team in University (IRT1252) and the Fundamental
Research Funds for the Central Universities are gratefully
acknowledged.
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