Construction and Building Materials 284 (2021) 122752

Contents lists available at ScienceDirect

Construction and Building Materials

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

Development of eco-friendly fire-retarded warm-mix epoxy asphalt

binders using reactive polymeric flame retardants for road tunnel
pavements
Ru Chen a, Ruikang Zhao a, Ya Liu a, Zhonghua Xi b, Jun Cai c, Junsheng Zhang a, Qingjun Wang a,⇑,
Hongfeng Xie a,⇑
a
MOE Key Laboratory of High Performance Polymer Materials and Technology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
b
Experimental Chemistry Teaching Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
c
Public Instrument Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, 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

Eco-friendly fire-retarded warm-mix

epoxy asphalt binders (WEABs) have
been developed.

RPFR of significantly improved the
fire retardancy of the pure WEAB.

RPFR hinders WEAB’s cure reaction
and extends the allowable
construction time of WEAB mixtures.

RPFR improves the glass transition
temperature and thermal stability of
the pure WEAB.

Double phase separation forms in
RPFR modified WEABs.

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

Article history: Epoxy asphalt binder is flammable and plenty of fumes are produced during its high-temperature pave-
Received 21 December 2020 ments in tunnels. To improve fire retardancy and reduce asphalt fumes, eco-friendly flame-retarded
Received in revised form 28 January 2021 warm-mix epoxy asphalt binders (WEABs) for road tunnel pavements were developed by incorporation
Accepted 17 February 2021
of reactive polymeric flame retardant (RPFR), which was composed of a reactive polymeric brominated
Available online 5 March 2021
epoxy oligomer (BEO) and antimony oxide. The influence of RPRF on flame retardancy, rotational viscos-
ity, microstructures, thermal properties and mechanical performance of the pure WEAB was investigated
Keywords:
using various techniques: oxygen index instrument, Brookfield viscometer, confocal microscope, differ-
Epoxy asphalt
Brominated flame retardant
ential scanning calorimeter, thermogravimetric analyzer and universal testing machine. The presence
Polymeric flame retardant of RPFR significantly improved the limited oxygen index (LOI) of the pure WEAB. The LOI of RPFR mod-
Limited oxygen index ified WEABs increased in the flame retardant loading. The reaction of epoxide groups of RPFR with the
Phase separation curing agents of epoxy asphalt reduced the viscosity of the pure WEAB and extended the allowable con-
Glass transition temperature struction time of the WEAB mixture. The inclusion of RPFR increased the glass transition temperature (Tg)
Thermal stability of the pure WEAB. For modified WEABs, the Tg increased in the RPFR loading. RPFR reacted into the epoxy
Mechanical properties asphalt backbone through the reaction between epoxy groups and curing agents. The incorporation of
RPFR improved the thermal stability of the pure WEAB. The addition of 8 wt% RPFR increased the tensile
strength of the pure WEAB, while the inclusion of RPFR slightly decreased the break elongation of the
pure WEAB. Double phase separation occurred in RPFR modified WEAB: the main phase separation

⇑ Corresponding authors.
E-mail addresses: njuwqj@nju.edu.cn (Q. Wang), hfxie@nju.edu.cn (H. Xie).

https://doi.org/10.1016/j.conbuildmat.2021.122752
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

included the continuous epoxy phase and the discontinuous asphalt domains, in which the secondary
phase separation formed with asphalt as the continuous phase and spherical BEO domains as the discon-
tinuous phase. The particle size of BEO domains decreased with the increase of the RPFR loading.
Ó 2021 Elsevier Ltd. All rights reserved.

1. Introduction Hot mix asphalt (HMA) pavements are widely utilized in road
construction. Due to the high production and pavement tempera-
Road tunnel construction is increasing day by day all over the ture (above 140 °C), however, a massive amount of energy is con-
world because it offers many conveniences to production and life. sumed and a great deal of asphalt fumes are generated and
China is the country with the longest total length and the largest released into the air [16,17]. Generally, asphalt fumes are a mixture
number of tunnels in the world. According to the Statistical Bul- of different compounds, including volatile organic compounds
letin on the Development of the Transportation Industry, 19,067 (VOCs), polycyclic aromatic hydrocarbons, sulfur, carbon monox-
road tunnels with a total mileage of 18999.6 km have been built ide, nitrogen oxides and particulates [18]. These compounds not
by the end of 2019 in China [1]. The rapid development of tunnel only influence the surrounding air quality but also may lead to
construction has aroused many concerns, especially for the life adverse health effects on workers dealing with asphalt. In particu-
safety of the occupants. Due to its good skid resistance, low noise lar, as one of the special atmospheric pollutants, VOCs can threaten
and ease of maintenance, more and more flexible bituminous pave- the health of the construction workers through both inhalation and
ments have been used in road tunnels [2,3]. However, the bitumi- skin contamination [19]. In the case of the road tunnel, because of
nous binder is flammable and its concrete is much easier to cause the confined space and the poor ventilation, pollutant gases
fire accidents than Portland cement concrete. In past decades, tun- released from HMA pavements are more harmful than conven-
nel fire accidents have resulted in human loss and injuries and tional HMA constructions in the open air. In this case, more and
major financial loss, which have imparted serious negative societal more warm-mix asphalt (WMA) mixtures combined with flame
impact [4,5]. Hence, worldwide tunnel safety professionals have retardant technology have been applied in road tunnels in China
paid much attention to the crucial design parameters for fire safety due to its benefit for the health of construction workers during
[6,7]. In order to enhance the fire resistance of road tunnel asphalt pavement, less fuel consumption and emissions of harmful gases
pavement, flame retardants have been introduced into the asphalt and fire retardancy [20–23].
binder [8,9]. Among all flame retardants, brominated chemicals are Epoxy modified asphalt, generally shortened as epoxy asphalt,
the most common-used ones because of their lower decomposition is one of the thermosetting polymer modified asphalts. Unlike
temperature and higher free radical trapping efficiency of bromine thermoplastic polymer modified asphalts, the base asphalt is
[10]. Brominated flame retardants are classified into three groups: mixed with low-molecular-weight epoxy components, including
additive, reactive and polymeric on account of their mode of addi- epoxy oligomers and curing agents [24–26]. The chemical reaction
tion into polymers. Due to their low molecular weight and no that occurred between epoxy components results in the formation
interaction with polymers, additive brominated flame retardants of three-dimensional crosslinking networks among the asphalt.
can easily leak from polymers to the environment, resulting in con- Consequently, the thermoplastic nature of asphalt is completely
cern about persistence, bioaccumulation, and toxicity (PBT) [11]. altered. For this reason, epoxy asphalt mixture has better thermal
For this reason, several additive brominated flame retardants, stability, strength and durability in comparison to other thermo-
which were worldwidely utilized in the past, such as polybromi- plastic polymer modified asphalt mixtures [27–29]. Therefore,
nated diphenyl ethers, polybrominated biphenyls and hexabromo- epoxy asphalt has been widely utilized as the binder in many spe-
cyclododecane are under vigorous regulatory scrutiny and have cial constructions, such as long-span orthotropic steel bridges, por-
been phased out [12]. On the other hand, thanks to their chemical ous pavements with high durability, road tunnels and airfield [30–
reaction with polymers, reactive flame retardants are more stable 32]. However, because of the intrinsic flammability of both asphalt
and hardly released into the environment [13]. Finally, since bro- and epoxy resin, epoxy asphalt is as combustible as asphalt and
mine atoms are in the backbone of polymeric structures, polymeric releases more smoke and poisonous gases during burning
flame retardants are less likely to leach out of the main polymer [14,33]. Therefore, it is of great importance to develop flame-
and also are less possible to be bioaccumulated by living organisms retarded epoxy asphalt binders for road tunnel pavements.
because of their bigger molecular weight [14]. Therefore, despite Similar to traditional asphalt binders, epoxy asphalt binders are
PBT concerns, brominated flame retardants are still used nowa- divided into three classes depending on paving temperatures:
days, but with more concentration on reactive and polymeric ones. cold-mix (ambient temperature), warm-mix (110–140 °C) and
As one of the polymeric flame retardants, brominated epoxy oli- hot-mix (160–190 °C) epoxy asphalt binders [34–36]. The paving
gomer (BEO), also named tetrabromobisphenol A diglycidyl ether, temperature of warm-mix epoxy asphalt concrete is 50–60 °C
has been widely used in printed circuit boards, styrenic resins and lower than that of hot-mix epoxy asphalt concrete. It is well
engineering plastics due to its high thermal stability, good impact accepted that the emission during asphalt production is highly
resistance, high mechanical stability, and excellent chemical resis- dependent on temperature [37]. Thus, this temperature reduction
tance [15]. Despite several preparation methods, the main way may cause a 20%–25% decline of dust, a 50% decline of VOC, a
involves the reaction between tetrabromobisphenol A diglycidyl 30%–40% decline of CO2, a 60% decline of NO2, a 10%–30% decline
ether and epichlorohydrin, which obtains materials with molecular of CO and a 35% decline of SO2 [38]. Meanwhile, fuel consumption
weights ranging from 1600 to 60,000 and bromine contents from is declined. So, warm-mix epoxy asphalt technology follows the
52% to 54%. Unlike other polymeric flame retardants, such as bromi- tendency of eco-friendly and sustainable development of road
nated polystyrene and poly(2,6-dibromophenylene oxide), BEO is a infrastructures.
reactive flame retardant when the oligomer terminates with two The objective of this study is to develop an eco-friendly flame-
epoxide groups at the chain end [13]. Thus, from the environmental retarded warm-mix epoxy asphalt binder (WEAB) for road tunnel
viewpoint, BEO is eco-friendly and highly effective due to its both pavements. To obtain this goal, a reactive polymeric flame retar-
reactive and inherently flame-retarded polymeric structures. dant (RPFR) system, BEO synergized with antimony oxide (AO)

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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Fig. 1. Chemical structure of BEO.

Fig. 2. Schematic illustration for the preparation of RPFR modified WEAB.

was introduced into the pure WEAB. The impact of the RPFR con- sents the schematic illustration for the preparation of RPFR modi-
tent on fire retardancy, viscosity, thermal behavior and mechanical fied WEAB.
performance of the pure WEAB were studied. Meanwhile, the
phase-separated morphologies of the pure and RPFR modified 2.3. Methods
WEABs were compared using laser scanning confocal microscopy
(LSCM). 2.3.1. Limited oxygen index (LOI)
An HC-2C oxygen index instrument (Nanjing Shangyuan Ana-
2. Materials and methods lytical Instrument Co. Ltd., China) was used to determine LOI val-
ues. The sample sheets of 100104 mm3 were tested under the
2.1. Materials guidance of ASTM D2863.

WEAB is composed of Part A (bisphenol A epoxy oligomers) and

2.3.2. Rotational viscosity
Part B (the mixture of acid-based curing agent and base asphalt
The viscosities of RPFR modified WEABs were tested with an
with a weight ratio of 2.65:3.25). The weight ratio of Part A and
NDJ-1C Brookfield viscometer (Shanghai Changji Instrument Co.
Part B is 1:5.9. Epoxy oligomers with an epoxy equivalent weight
Ltd., China) with the 28# spindle under a rotational speed of
of 185–194 g/eq were obtained from Nantong Xingchen Synthetic
50 rpm. The viscosity was recorded at a 5-min interval at 120 °C
Material Co., Ltd., China. 80/100 penetration grade base asphalt
until it reached 10000 mPas in the light of ASTM D4402.
was provided by China Offshore Bitumen (Taizhou) Co., Ltd. Table 1
presents the overview of the base asphalt. The acid-based curing
agent was self-synthesized. RPFR is composed of BEO and AO 2.3.3. Differential scanning calorimetry (DSC)
(Sb2O3) with a weight ratio of 3:1. BEO (NPEB-400) was supplied The glass transition temperatures (Tgs) of RPFR modified WEABs
by Nan Ya Plastics Corporation, Taiwan, China. The EEW and bro- were evaluated with a Mettler Toledo DSC 1 (Leicester, UK). A sam-
mine content of BEO are 380–420 g/eq and 46–50%, respectively. ple with approximately 5 mg was heated at a temperature range of
Fig. 1 shows the chemical structure of the BEO. AO with an average 0–80 °C with a heating rate of 20 K min1 from under the protec-
particle size of 0.5–1.3 mm was manufactured by Jinan Taixing Fine tion of nitrogen purge (20 mL min1). To eliminate the effect of
Chemical Co. Ltd., China. The purity of AO is over 99.8%. thermal history [39], Tg was taken as the point of the intersection
of the DSC curve with the bisector of the angle between the two
2.2. Sample preparation baselines in the heating step of the second run [40].

RPFR was added into Part B in a 250-mL beaker and mixed by a 2.3.4. Infrared (IR) spectroscopy
Fluko FM300 mixer (Fluko Company, Shanghai, China) with a rota- Fourier transform infrared (FTIR) spectra were obtained from an
tional speed of 4000 rpm at 120 °C for 30 min. Then, Part A was FTIR spectrometer (Nexus 870, Nicolet). KBr pellets of BEO and
introduced into the mixture of RPFR and Part B, followed by uncured RPFR modified WEAB were scanned in the wavenumber
mechanical mixing at 200 rpm for 5 min at 120 °C and cured in a range of 4000–400 cm1. For the FTIR spectrum of the cured sam-
Teflon mold at the same temperature for 4 h. The RPFR contents ple, the KBr pellet of the uncured RPFR modified WEAB was cured
in the WEABs are 0, 4, 8, 12, 16 and 20 wt%, respectively. Fig. 2 pre- at 120 °C for 4 h.
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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Table 1
Overview of base asphalt.

Properties 80/100 Test standard

Penetration (25 °C, 0.1 mm) 91 ASTM D5
Ductility (10 °C, cm) 93.0 ASTM D113
Softening point (°C) 46.3 ASTM D36
Viscosity (120 °C, mPa∙s) 787 ASTM D 4402
Saturates (wt%) 16.7 ASTM D4124
Aromatics (wt%) 33.9
Resins (wt%) 44.7
Asphaltenes (wt%) 4.7

2.3.5. Thermogravimetric analysis (TGA)

A simultaneous TGA/DSC (Mettler Toledo TGA/DSC 1) was used
to characterize thermal stability. A sample of approximate weight
10 mg was heated under the protection of a nitrogen purge
(40 mL min1) from 50 to 700 °C at a ramp rate of 20 K min1.
Fig. 3. LOIs of the pure and RPFR modified WEABs.

2.3.6. Mechanical performance

Tensile strength and break elongation of the pure and modified produced through the highly exothermic oxidation between CO
WEABs were tested with a universal test machine (UTM, Instron and hydroxyl radicals:
3366, Norwood, MA, USA) under the guidance of ASTM D638 (Type
V). Five samples from each batch were measured at room temper-
OH + CO = CO2 + H ð1Þ
ature with a crosshead speed of 200 mm min1.
H + O2 = OH: + O ð2Þ

2.3.7. LSCM Halogen-containing flame retardants release hydrogen halide in

The fluorescent images were taken using a confocal microscope the flame zone, which reacts with the active hydrogen and hydro-
(Carl Zeiss, LSM710, Jena, Germany). To prepare the sample for xyl radicals and produces the less active halogen radicals [10]:
LSCM observation, the uncured sample was dissolved overnight
in toluene to obtain a solution of 2 g mL1. Afterward, a drop of
H + HX = X + H2 ð3Þ
solution was dripped on a microscope slide and spun at
3000 rpm for 1 min. In order to remove toluene, the slide was HX + OH = X + H2 O ð4Þ
heated in an oven at 115 °C for 3 min [41]. Finally, a cover glass
Furthermore, halides are nonflammable gases, which can dilute
was covered and the sample slide was cured at 120 °C for 4 h.
flammable gases. The synergistic effect of the halogen-antimony
combination is due to the production of SbX3 via the reaction
3. Results and discussion between HX and Sb2O3. In comparison to HX, SbX3 is a more
effective flame inhibitor [46]. In addition, a carbonaceous residue
3.1. LOI produced by SbX3 is favorable for promoting the dehydrohalogena-
tion of the halogen-containing flame retardants along with rear-
As one of the most common and widespread tools, LOI measure- rangement and coupling reactions in organic systems [47].
ment is often used to evaluate the effectiveness of flame retardants Therefore, due to the synergistic effect of halogen-antimony com-
and the intrinsic flammability of a material [42]. The greater the pounds, the flame retardancy of the pure WEAB is greatly
LOI value, the better is the intrinsic fire resistance. Generally, the improved with a lower RPFR loading. Kaynak and Isitman revealed
LOI value of flammable material is lower than 22%, while a material that the inclusion of the flame retardant composed of BEO, AO and
becomes flame-retardant when the LOI value is more than 27%. At hydrated calcium borate with the weight ratio of 23:3:1 increases
the intermediate LOI range (22–27%), a material is hard to combust the LOI of neat high-impact polystyrene only to 25.8% [48].
[43]. Fig. 3 presents LOIs of the pure and RPFR modified WEABs. However, with the addition of 12 wt% RPFR, only less than one-
The LOI of the pure WEAB is only 24.1%. It needs to point out that second of the mixture of BEO, AO and hydrated calcium borate,
the pure WEAB has a greater LOI (24.1%) than the neat epoxy and the LOI of the pure WEAB increases to 29.9%. Consequently, the sig-
CEAB, whose LOI values are 20.5% and 20.0%, respectively since nificant LOI increase of RPFR modified WEABs with a lower flame
more char residues form in the pure WEAB, which hinders the retardant loading may be also correlated to the interaction
propagation of the fire [33,44]. The inclusion of RPFR increases between BOE and the epoxy asphalt.
the LOI value of the pure WEAB. In terms of modified WEABs, the
LOI linearly increases in the RPFR content from 24.3% to 32.0%, 3.2. Rotational viscosity-time behavior
revealing that RPFR improves the fire resistance of the pure WEAB.
Especially when adding over 12 wt% RPFR, the LOI value is 29.9%, As a thermoplastic material, the viscosity of conventional
indicates that the modified WEAB becomes flame-retardant. Corre- asphalt mainly relates to temperature. Due to its thermosetting
spondingly, flame-retardant WEAB is very crucial to the mixtures feature, however, the viscosity of epoxy asphalt depends on both
used in road tunnels. Similar LOI value was also reported in a RPFR the temperature and the time. Therefore, the relationship of viscos-
modified poly(butylene terephthalate) with 19 wt% flame retar- ity between both curing time and temperature becomes a key tech-
dant [45]. nical index for epoxy asphalt construction [49,50]. Fig. 4 illustrates
It is believed that hydrogen and hydroxyl radicals are of great viscosity-curing time plots of the pure and RPFR modified WEABs
importance for sustaining ignition. Oxygen is consumed by at 120 °C. Owing to the instability in the initial stage of the cure
hydrogen radicals via branching reaction in the flame and CO2 is reaction, all viscosities reduce within 5 min [51]. The viscosity
4
R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

It is of note that the reaction between the epoxide groups of the

polymeric flame retardant and curing agent of epoxy asphalt
results in the fact that reactive BEO becomes a part of the polymer
backbone and thus greatly diminishes the probability of flame
retardants migrating out of the epoxy asphalt and releasing into
the environment in comparison to an individual reactive or poly-
meric flame retardant.
In light of the technical guideline of epoxy asphalt binders for
roads and bridges, it is stipulated that the time for the binder vis-
cosity to reach 1 Pas should be less than 40 min [55]. As illustrated
in Table 2, the time for the viscosity to reach 1 Pas of the pure
WEAB is 44 min. Evidently, the viscosities of RPFR modified WEABs
take a longer time to reach 1 Pas, which indicates the presence of
RPFR extends the allowable construction time and lowers the con-
struction difficulty of mixture pavements. Additionally, in terms of
the viscosities of RPFR modified WEABs, the time to reach 1 Pas
Fig. 4. Rotational viscosity-time curves of the pure and RPFR modified WEABs. increases in the flame retardant content.

3.3. Morphology
increases slowly along with the curing time in the range of 5–
40 min. RPFR has a marginal effect on the viscosity of the pure Because of its higher depth discrimination in comparison to flu-
WEAB. After 40 min, the viscosity increases sharply due to the orescence microscopy, LSCM is an important tool to explore the
gelation of epoxy resin. In the meantime, the viscosity of the pure phase-separated morphologies of polymer blends and polymer
WEAB is higher than those of RPFR modified WEABs at a specific modified asphalts [56,57]. Fig. 6 presents LSCM images with
curing time, revealing that RPFR hampers the chemical curing of 100 magnifications of the pure and RPFR modified WEABs.
the pure WEAB. In terms of RPFR modified WEABs, the hindrance Clearly, the reaction-induced phase separation takes place, giving
effect increases in the flame retardant loading. Similar trends were rise to the formation of the sea-island morphology in both pure
also observed in nanoclay modified epoxy asphalts [52,53]. How- WEAB and RPFR modified WEABs. In other words, islands of spher-
ever, an opposite trend appeared in another antimony-halogen ical asphalt domains disperse in the sea of epoxy resin. It is worthy
system (decabromodiphenyl ethane/AO) modified WEAB [54], to note that the diameters of asphalt particles in the epoxy matrix
which unavoidably shortens the construction time and increases of RPFR modified WEABs are much smaller than those of the pure
the construction difficulty of mixture pavements. WEAB. The reduction of asphalt domain size may be attributed to
To investigate the effect of RPFR on the cure reaction of the pure the cure reaction between epoxy groups of BOE and curing agents
WEAB, FT-IR spectroscopy was used. Fig. 5 shows FTIR spectra of of the epoxy asphalt, which restricts the asphalt particles to coa-
BEO and the modified WEAB with 4 wt% RPFR before and after cur- lesce to larger ones.
ing. For BEO and the uncured RPFR modified WEAB, the specific In order to determine the dispersion of asphalt particles in the
peaks for epoxide groups appear at 910 cm1 and 917 cm1, continuous epoxy phase of the pure and RPFR modified WEABs,
respectively. After the cure reaction, however, the specific peak area fractions, domain size distributions and average diameters
for epoxide groups disappears, which means that RPFR takes part of asphalt phase in the continuous epoxy phase were obtained
in the cure reaction of epoxy asphalt through the reaction of epox- from LSCM images with 100 magnifications by using professional
ide groups of BEO with the curing agent of the epoxy asphalt. These image software. Fig. 7 presents area fractions of asphalt domain in
reactions delay the cure reaction of RPFR modified epoxy asphalts the pure WEAB and RPFR modified WEABs. The area fraction of the
and thus lead to the viscosity decrease of RPFR modified WEABs in asphalt phase in the pure WEAB is 48.3%, which is very close to the
comparison to the pure WEAB as shown in Fig. 4. weight ratio of asphalt (47.1%). The existence of RPFR lowers the
area fraction of the pure WEAB. The reaction between the epoxide
groups of BEO and the curing agents of epoxy asphalt leads to the
increase of crosslink density and some BEO particles transferring to
the continuous epoxy phase. In the case of RPFR modified WEABs,
when adding less than 12 wt% RPFR, the flame retardant loading
has a marginal effect on the area fraction, which is in the range
of 37%-38%. A maximum value appears at 16 wt% RPFR (46.8%)
and then the area fraction decreases to 42.1%. These results indi-
cate that more BEO transfers to the continuous epoxy phase when
the RPFR loading is lower than 12 wt%.
Size distributions of asphalt domains in the pure and RPFR mod-
ified WEABs are depicted in Fig. 8. The asphalt domain size distri-
bution of the pure WEAB is wide. However, RPFR modified WEABs
exhibit narrower domain size distribution, which mainly varies
between 10 lm and 20 lm.
Table 3 lists average diameters and polydispersity indexes
(PDIs) of the pure and RPFR modified WEABs. Evidently, the exis-
tence of RPFR significantly decreases the average diameters of
the pure WEAB, whose dn (number-average diameter) and dw
(weight-average diameter) are 25.9 lm and 41.4 lm, respectively.
Fig. 5. FTIR spectra of BEO and the modified WEAB with 4 wt% RPFR before and Similar outcomes were also reported in SBS modified epoxy
after curing. asphalts [35,57]. In terms of RPFR modified WEABs, the average
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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Table 2
The time for the viscosity to reach 1 Pas for the pure and RPFR modified WEABs.

Sample RPFR (wt%)

0 4 8 12 16 20
Time (min) 44 46 48 48 49 49

Fig. 6. LSCM images (100) of the pure WEAB (a) and RPFR modified WEABs: 4 wt% RPFR (b), 8 wt% RPFR (c), 12 wt% RPFR (d), 16 wt% RPFR (e) and 20 wt% RPFR (f).

Fig. 7. Area fractions of asphalt domains in the pure and RPFR modified WEABs. Fig. 8. Asphalt domain size distributions of the pure and RPFR modified WEABs.

diameter decreases in the flame retardant content. On the contrary, circumstance, the average diameters of the asphalt phase become
both EVA and SBS modified epoxy asphalts exhibit an opposite smaller. PDI, the ratio of dw and dn, indicates the homogeneity of
trend [57,58]. It is acknowledged that thermoplastic polymers, particle size. The higher the PDI value, the more homogeneous
such as EVA and SBS, absorb light components of asphalt and thus the particle size. As shown in Table 3, the inclusion of RPFR slightly
swell in the asphalt. However, BEO is a lower molecular-weight declines the PDI value of the pure WEAB, indicating that asphalt
polar polymer, which cannot absorb the maltenes of asphalt. In this domains disperse more uniformly in RPFR modified WEABs. For

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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Table 3 Table 4
Average diameters and PDIs of the pure and RPFR modified WEABs. Average diameters and PDIs of BEO domains in the secondary asphalt phase.

RPFR (wt%) dn (lm) dw (lm) PDI RPFR (wt%) dn (mm) dw (mm) PDI
0 25.9 41.4 1.60 4 4.3 5.7 1.33
4 17.1 23.3 1.36 8 3.5 4.1 1.17
8 17.0 22.2 1.31 12 4.1 5.1 1.24
12 14.0 19.8 1.41 16 2.9 3.2 1.10
16 13.2 17.6 1.34 20 2.8 3.0 1.07
20 12.6 16.9 1.34

The dn of BEO domains varies from 3 lm to 4 lm, while the dw is in

RPFR modified WEABs, the flame retardant content has a limited the range of 3–6 lm. Apart from the 8 wt% loading, both average
effect on the PDI value. diameters and PDIs of spherical BEO domains decrease in the RPFR
To further observe the discontinuous asphalt particles in the loading, indicating that BEO domains disperse more uniformly
continuous epoxy matrix, magnified LSCM micrographs (400) with the increase of the flame retardant loading. In contrast, the
were taken. As shown in Fig. 9, interestingly, differing from the average diameters of nonpolar SBS domains in the asphalt phase
pure WEAB, another sea-island morphology forms in the discontin- of SBS modified epoxy asphalts increase in the polymer loading
uous asphalt domains. As one of the polymeric flame retardants [57]. The diameter decrease of BEO domains in the asphalt phase
[47], part of BEO disperses and gathers to spherical particles (is- with the increase of the flame retardant loading is attributed to
lands) in the asphalt phase (sea), which indicates that BEO and the polarity and steric effect of BEO, which restrict the merge of
asphalt are immiscible. This double phase separation generally spherical domains to larger ones.
appears in the asphalts modified by polymers, such as ethylene
vinyl acetate copolymer (EVA), styrene–butadienestyrene copoly-
mer (SBS) and brominated SBS [14,35,41,56,58]. That is to say, 3.4. Glass transition
polymer modified asphalts act as the secondary phase separation
in these polymer modified epoxy asphalt binders. In the core–shell DSC thermograms of the pure and RPFR modified WEABs are
rubber modified epoxy asphalt, on the contrary, polymer domains depicted in Fig. 10. Only one Tg exhibits in the pure WEAB and
mainly disperse in the continuous epoxy phase [59]. It is important RPFR modified ones. As shown in Table 5, the Tg of the pure WEAB
to mention that the difference in the dispersion of polymer is 18.3 °C. The inclusion of RPFR increases the Tg value of the pure
domains in the continuous or discontinuous phase of the epoxy WEAB. For RPFR flame-retarded WEABs, as shown in Table 5, the Tg
asphalt affects significantly the mechanical properties of the epoxy increases in the flame retardant content.
asphalt as discussed later. It is believed that the Tg of an epoxy material depends on the
Table 4 summarizes average diameters and PDIs of BEO crosslinking density [60,61]. Therefore, the Tg improvement of
domains in the secondary asphalt phase of RPFR modified WEABs. RPFR modified WEABs is attributed to the fact that the reactive

Fig. 9. LSCM images (400) of the pure WEAB (a) and RPFR modified WEABs: 4 wt% RPFR (b), 8 wt% RPFR (c), 12 wt% RPFR (d), 16 wt% RPFR (e) and 20 wt% RPFR (f).

7
R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Fig. 10. DSC thermograms of the pure and RPFR modified WEABs.

epoxide groups of BEO in RPFR react with the curing agent of the
epoxy asphalt. It is known that the crosslink density of epoxies
depends on the stoichiometry of epoxy oligomers/curing agents
[62]. Excess epoxy oligomers increase the crosslink density and
thus increase the Tg of epoxies. The reaction of epoxide groups of
BEO in RPFR with the curing agents of the epoxy asphalt gives rise
to the excess epoxy oligomers and the increase of the crosslink
density. In this case, the inclusion of RPFR increases the Tg of the
pure WEAB.

3.5. Thermal stability

Fig. 11. TGA and DTG thermograms of BE, AO and RPFR.
TGA and derivative thermogravimetric (DTG) thermograms for
BEO, AO and RPFR are illustrated in Fig. 11. Both BEO and AO
undergo a single-step thermal degradation, which takes place in dants. What’s more, the peak of maximal decomposition at the first
the temperature range of 250–400 °C and 550–700 °C, respectively. step becomes bigger, while the corresponding peak at the second
For RPFR, a two-stage thermal decomposition occurs. The main stage turns to be smaller with the increase of the RPFR content.
pyrolysis takes place from 250 °C to 450 °C, while the minor Thermal parameters of the pure and RPFR modified WEABs are
decomposition appears in the temperature range of 500–600 °C. listed in Table 7. Clearly, the presence of RPFR increases the Ti, T1max
Table 6 summarizes TGA and DTG results of all flame retar- and the maximal decomposition rate at the second step (T2max) values
dants. The initial degradation temperatures (Tis, the temperatures of the pure WEAB, which manifests that RPFR improves the ther-
at 95% weight) of BEO and AO are 313.9 °C and 565.0 °C, respec- mostability of the pure WEAB. Furthermore, the thermal stability
tively, while the Ti of RPFR (336.4 °C) is in the middle of these of of RPFR modified WEABs increases in the RPFR content. Similar trend
BEO and AO. The temperature of the maximal decomposition rate was also found in the RPFR modified poly(butylene terephthalate)
at the first step (T1max, 373.9 °C) of RPFR is lower than those of both blends [45]. On the contrary, the thermal stability of long-glass-
BOE and AO (379.5 °C and 668.6 °C). Noting that the char at 700 °C of fiber reinforced polyamide 6 was weakened by the addition of RPFR
RPFR (26.5%) is much higher than those of BEO and AO due to the [64]. The improvement of thermal stability attributes to the reaction
fact that the reaction between hydrogen halide and AO produces between epoxide groups of BEO and curing agents of the epoxy
more carbonaceous residue as mentioned previously. asphalt, leading to an increase of crosslink density of the pure WEAB
Fig. 12 depicts TGA and DTG curves of the pure and RPFR mod- as discussed above. In contrast, the addition of RPFR sacrifices the
ified WEABs. The pyrolysis process of the pure WEAB includes two thermal stability of high-impact polystyrene since there is no reac-
stages. The first stage occurs in the temperature range of 200– tion between the reactive flame retardant and the polymer matrix
360 °C. In this stage, unreacted epoxy and light components of [48]. The inclusion of RPFR also increases the char at 700 °C of the
asphalt are lost. The second stage (main decomposition stage) is pure WEAB. Additionally, the char at 700 °C of RPFR modified WEABs
from the end of the first step to 510 °C. Most of the organic species increases in the flame retardant content. As discussed previously, the
of epoxy networks and asphalt degrade in this step [63]. In terms of char increase is beneficial for the improvement of fire retardancy.
RPFR modified WEABs, the first step from 200 to around 400 °C Consequently, the increasing trend of char at 700 °C for RPFR modi-
shifts to higher temperature due to the existence of flame retar- fied WEABs agrees well with that of LOI as shown in Fig. 3.

Table 5
Tgs of the pure and RPFR modified WEABs.

Sample RPFR (wt%)

0 4 8 12 16 20
Tg (°C) 18.3 20.1 20.4 20.6 20.9 21.1

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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

Table 6
TGA and DTG data of the flame retardants.

Sample Ti (°C) T1max (°C) T2max (°C) Char at 700 °C(%)

BEO 313.9 379.5 – 9.3
AO 565.0 668.6 – 10.4
RPFR 336.4 373.9 562.6 26.5

Fig. 13. Tensile strength (a) and break elongation (b) of the pure and RPFR modified
WEABs.

tensile strength the pure WEAB since no reaction takes between

decabromodiphenyl ethane and epoxy asphalt [54]. The increase
of the tensile strength for the pure WEAB at a lower RPFR loading
is due to the fact that more reactive BEO participates in the cure
reaction of epoxy asphalt and moves to the continuous epoxy
phase as shown in Fig. 9, resulting in the increase of crosslinked
Fig. 12. TGA and DTG curves of the pure and RPFR modified WEABs.
epoxy networks [65]. Correspondingly, the tensile strength of RPFR
modified WEABs decreases when less reactive BEO joins the cure
3.6. Mechanical properties reaction of epoxy asphalt and moves to the continuous epoxy
phase. However, since more BEO particles disperse in the asphalt
Tensile strengths and break elongations for the pure WEAB and phase, the tensile strength of RPFR modified WEABs decreases in
RPFR modified WEABs are shown in Fig. 13. As illustrated in the flame retardant loading.
Fig. 13a, the effect of RPFR on the tensile strength of the pure WEAB As illustrated in Fig. 13b, in contrast to tensile strength, the
depends on the flame retardant content. When the flame retardant addition of RPFR slightly reduces the break elongation of the pure
concentration is less than 8 wt%, the incorporation of RPFR results WEAB due to the brittle nature of BEO. Similarly, the presence of
in a slight increase of the tensile strength of the pure WEAB, which RPFR greatly declines the break elongation of poly(butylene
is attributed to the dispersion of RPFR in the epoxy asphalt as dis- terephthalate) [45]. For RPFR modified WEABs, the break elonga-
cussed previously. However, the opposite trend appears when the tion decreases in the flame retardant content when the RRF con-
RPFR content is over 8 wt%. Quite different from the BOE/AO sys- tent is lower than 8 wt%. However, when adding over 8 wt%
tem, the addition of decabromodiphenyl ethane/AO lowered the RPFR, a contrary trend comes out.

Table 7
TGA and DTG data of the pure and RPFR modified WEABs.

RPFR (wt%) Ti (°C) T1max (°C) T2max (°C) Char at 700 °C (%)
0 282.4 328.7 448.6 5.3
4 286.2 374.4 451.3 6.6
8 286.4 353.6 452.1 8.1
12 289.2 354.3 458.7 8.3
16 294.9 354.8 452.3 8.5
20 296.5 356.7 466.5 8.6

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R. Chen, R. Zhao, Y. Liu et al. Construction and Building Materials 284 (2021) 122752

(1) RPFR significantly enhances the fire retardancy of the neat

WEAB. The LOI value of the pure WEAB increases from
24.1% to 32.0% with the addition of 4 wt%-20 wt% RPFRs.
(2) RPFR has a limited effect on the viscosity of the pure WEAB
at 120 °C before 40 min, while the viscosity of RPFR modified
WEABs is lower than that of the pure WEAB after 40 min. In
addition, the viscosity of RPFR modified WEABs decreases in
the flame retardant loading.
(3) Double phase separation forms in RPFR modified WEABs, i.
e., spherical BEO particles disperse in the asphalt phase,
which acts as the dispersed phase of the modified WEABs.
The particle size of asphalt domains in the pure WEAB is
declined with the addition of RPFR. The average diameters
of BEO particles in the asphalt phase decrease in the flame
retardant concentration.
(4) The presence of RPFR improves the Tg and thermal stability
of the neat WEAB. For modified WEABs, both Tg and thermal
stability increases in the RPFR loading.
(5) The incorporation of RPFR improves the tensile strength of
the pure WEAB when adding 8 wt% RPFR, while RPFR lowers
the break elongation and toughness of the pure WEAB. The
existence of RPFR has a negligible effect on the Young’s mod-
ulus of the pure WEAB. All tensile properties of RPFR modi-
fied WEABs satisfy the technical guideline of epoxy asphalt
binder for road and bridge pavements.

CRediT authorship contribution statement

Ru Chen: Conceptualization, Investigation, Formal analysis,

Data curation. Ruikang Zhao: Investigation. Ya Liu: Investigation.
Zhonghua Xi: Resources. Jun Cai: Resources. Junsheng Zhang:
Fig. 14. Toughness (a) and Young’s modulus of the pure and RPFR modified WEABs. Investigation. Qingjun Wang: Supervision. Hongfeng Xie: Super-
vision, Writing - original draft, Writing – review & editing.

In light of the technical guideline of epoxy asphalt binders for

pavements of roads and bridges, the TS and EB should be over Declaration of Competing Interest
1.5 MPa and 200%, respectively [55]. It is evident that all tensile
properties of RPFR modified WEABs meet this guideline. The authors declare that they have no known competing finan-
Fig. 14 illustrates toughness and Young’s modulus of the pure cial interests or personal relationships that could have appeared
and RPFR modified WEABs. Unlike other BEO modified epoxies to influence the work reported in this paper.
[66], as shown in Fig. 14a, the inclusion of RPFR lowers the tough-
ness (fracture energy) of the pure WEAB. For RPFR modified
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