Fuel 85 (2006) 1298–1304

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Experimental investigation of related properties of asphalt binders

containing various flame retardants
Shaopeng Wu a,*, Peiliang Cong a, Jianying Yu a, Xiaofeng Luo a, Liantong Mo a,b
a
Key Laboratory of Silicate Materials Science and Engineering, Wuhan University of Technology, Ministry of Education, Wuhan 430070, China
b
Road and Railway Engineering, Civil Engineering and Goesciences, Delft University of Technology, Delft 2600GA, The Netherlands
Received 27 January 2005; received in revised form 10 May 2005; accepted 24 October 2005
Available online 16 November 2005

Abstract
The improved flame retardancy of asphalt binders containing various kinds of flame retardants including antimony trioxide, decabromodiphenyl
ether (EBPED), aluminium trihydroxide (ATH) and zinc borate (ZB) under different additive concentrations was investigated by limited oxygen
index (LOI) and differential scanning calorimetry (DSC) test. To assess the effects of the type and concentration of the flame retardants on
rheological properties of asphalt binders, the softening point, penetration, ductility, storage stability and viscosity were tested. The thin film oven
test (TFOT) was used to investigate the effect of short-term oxidation on flame-resistant asphalt binders. Experimental results indicated that all of
selected flame retardants had a relatively small effect of rheological properties of the asphalt binders, but a great effect on flame retardancy.
Asphalt binder with LOI of 25.9 was obtained by adding 6 wt% mixed flame retardants of EBPED: antimony trioxide: ZBZ3:1:1 by mass.
Asphalt binder was transformed from inflammable materials into flame retardant materials. Therefore, the asphalt binder with both good flame
retardancy and rheological properties is a novel road functional material to meet two respects’ demands as flame retardant materials and road
materials at the same time.
q 2005 Published by Elsevier Ltd.

Keywords: Asphalt; Flame-resistant; Rheological properties

1. Introduction flammability of asphalt materials. But the flame-resistant

Asphalt is a complex mixture of organic molecules that vary
in chemical compositions and molecular weights. As asphalt is
extracted from crude oil, which has many different compo-
sitions according to its origin, the precise breakdown of the
hydrocarbon groups in asphalt is difficult to determine.
Therefore, four main chemical types are used to classify the
compositions of the bitumen: asphaltenes, resins, aromatics
and saturates. It is mainly composed of saturates, naphthene
aromatics, polar aromatics and asphaltenes. So, the asphalt
materials are easy to burn at approximately 300 8C [1–3].
Asphalt can be applied as construction material in the field of
domestic and pavement buildings. An expanded growth of
asphalt application concurrent with the proliferation of safety
standards being set by government and private agencies has
indicated that it is of primary importance to reduce the
* Corresponding author. Tel./fax.: C86 27 87162595.
E-mail address: wusp@whut.mail.edu.cn (S. Wu).
0016-2361/$ - see front matter q 2005 Published by Elsevier Ltd.
doi:10.1016/j.fuel.2005.10.014
asphalt binders have been relatively little studied in the field
of asphalt pavement. The mechanism and compositions of
flame-resistant asphalt binders need to be investigated deeply.
Generally, five burning processes are considered to be
involved in asphalt flammability: heating, decomposition,
ignition, combustion and propagation. Flame retardancy can
be acquired by the disruption of the burning process at one or
more stages so that the process is terminated within an
acceptable period of time, preferably before ignition actually
occurs [4,5]. In this study, various kinds and concentrations of
flame retardants were added into the asphalt to cut out the
burning process of asphalt binders, acting as a role of flame
retardancy. It is well-know that all kinds of flame retardants
have respective flame-retardant mechanism, for example,
aluminium trihydroxide can decrease the surface temperature
and retard the pyrolysis of the polymer by its endothermic
decomposition and water release; Halogenated flame retardants
are postulated to function mainly by a vapour phase flame
inhibition mechanism through radical chain reaction. Zinc
borate can increase the conversion of polymer to a char residue
and reduces the formation of flammable carbon-containing
gases [6–15].
 S. Wu et al. / Fuel 85 (2006) 1298–1304 1299

In this paper, the effects of various flame retardants on flame Aging index : AI Z lg½lgðV2 !103 ÞKlg½lgðV1 !103 Þ (3)
retardancy of asphalt binders were studied by the limited
oxygen index (LOI) and evaluated other related properties by where P (0.01 mm), T ( 8C) and V (Pa.s) denote penetration,
laboratory tests to optimise the composite system of asphalt softening point and viscosity, respectively. The subscripts 1 and
and flame retardant. After preparing the flame-resistant asphalt 2 present unaged and aged flame-resistant asphalt binders.
binder, the related tests of the flame-resistant asphalt binders The storage stability of flame-resistant modified asphalt
including penetration, softening point, ductility, storage binders was tested as following procedure: before the sample
stability, viscosity and short-term aging properties were carried was poured into a glass tube, the inner wall of the glass tube
out. was coated a thin layer of isolated agent made by glycerine and
French chalk powders at the weight ratio 2:1. The tube was
sealed by soft tampion, and stored vertically and immovably in
2. Experimental
an oven at 163G5 8C for 48 h. Then the glass tube containing
the flame-resistant asphalt was took out of the oven and put into
2.1. Raw materials
an icebox for 4 hG5 min to solidify the sample. All glass tubes
were broke into pieces with a hammer carefully to remain
AH-70 paving asphalt was obtained from Koch Asphalt Co.
unbroken cylindrical asphalt samples, on which the isolated
Ltd in Hubei province, China, with penetration of 69 dmm at
agent was washed away. The cylindrical asphalt sample was
25 8C, ductility of greater 200 cm at 15 8C, softening point of
cut horizontally into three equal sections. The sections from the
44.8 8C, and viscosity of 0.45 Pa.s at 135 8C.
top and bottom were placed in separate dishes in an oven at
All of flame retardants were made in Taixing Industry of
163 8C until asphalt binder had well fluid to pour into softening
Fine Chemicals Co. Ltd in Jinan, China. The related properties
point rings. The difference in softening points between top and
of these flame retardants are as follows:
bottom sections as well as the change compared with the
Aluminium trihydroxide (ATH): density 2.42 g/cm3, maxi-
original asphalt was used to evaluate the storage stability, that
mum particle size 10 mm, pH!8.5.
is, the segregation of the flame retardant in the asphalt.
Zinc borate (ZB): density 2.67 g/cm3, maximum particle
Brookfield viscometer (Model DV-IIC, Brookfield Engin-
size 5 mm, maximum ignition loss 15.5%; Antimony trioxide:
eering, Inc., USA) was employed to measure the rolling
melting point 656 8C, maximum particle size 1.6 mm.
viscosity of modified asphalt binders in according to ASTM
Decabromodiphenyl ether (EBPED): density 3.25 g/cm3,
D4402. Approximately 30 g of asphalt were heated in an oven
maximum particle size 5 mm, minimum bromine concentration
so that it was sufficiently fluid to pour into the sample chamber.
of 82% and maximum free bromine concentration of 10%. The
The amounts of asphalt used varied with the different sizes of
melting temperature ranges from 300 to 310 8C and the
the spindles. The sample chamber containing the asphalt
pyrolysis temperature is 320 8C.
sample was then placed in the thermo container. After the
desired temperature was stabilized for about 30 min, the
2.2. Methods
spindle was lowered into the chamber to test the viscosity.
DSC thermograms were obtained using a PL-DSC made in
Asphalt was heated to 170G5 8C in an oil-bath heating
USA with a power compensation head. The test was carried out
container until it flowed fully. The appropriate amounts of
under flowing air of 10 ml/min and a heating rate of 10 K/min.
flame retardants presented in weight percentage of asphalt were
About 2.0 mg of sample was taken in each case and respective
mixed into a shear blender containing the preheated asphalt.
peaks were recorded.
Then the blender’s blade was inserted into the asphalt binder
Limiting oxygen index methods are widely used to measure
sample and operated under high rotate speed about 30–45 min
the flammability of polymers and to investigate the effective-
to ensure the well dispersion of flame retardants in asphalt
ness of flame retardants. Flame retardancy of asphaltbinders
binders.
was assessed by the limiting oxygen index according to ASTM
The rheological properties of asphalt binders, including
D-2863-77. Test procedures were as follows: the top of the
softening point, penetration and ductility, were tested in
sample was ignited by a gas flame which was stopped once
accordance with ASTM D36, ASTM D5 and ASTM D113-86,
ignition had occurred, and then the lowest oxygen concen-
respectively. The thin film over test (TFOT) was employed to
tration in a flowing mixture of nitrogen and oxygen which just
simulate the short-term oxidation that occurs during the hot mix
supports sustained burning can be determined. The effective-
process in accordance to ASTM D1754 [16]. The percent
ness of flame retardants was measured by the changes in the
retained penetration, viscosity ratio, aging index and increment
critical oxygen concentration. The limiting oxygen index (LOI)
of softening point all were used to evaluate relative aging degree
was defined as Eq. (4)
of asphalt binders modified by different flame retardants. The
related equations were expressed as follows Fcr ðO2 Þ
LOI Z (4)
P Fcr ðO2 Þ C FðN2 Þ
Percent retained penetration : PRP Z 2 !100% (1)
P1 where Fcr(O2) and F(N2) are the minimum oxygen concen-
tration and the relevant nitrogen concentration in the inflow
Increment of softening point : DT Z T2 KT1 (2) gases, respectively.
1300 S. Wu et al. / Fuel 85 (2006) 1298–1304

3. Results and discussion

3.1. Rheological properties and aging properties

Fig. 1 shows the softening points of the flame-resistant

asphalt binders change under the function of increasing flame
retardant concentration, which implies that high temperature
properties of asphalt would be improved by the addition of
flame retardants. When the concentration of EBPED plus
antimony trioxide is 6 wt%, the modified asphalt binder shows
higher softening point compared with original and other
asphalt binders. Other flame retardants, Zinc borate, antimony
trioxide and aluminium trihydroxide all have a similar effect on
softening point, which increases with increasing flame
retardant concentration. However, the change in softening
point of EBPED modified asphalt binders trend to saturate.
EBPED/antimony trioxide and EBPED/ZB/antimony trioxide Fig. 2. Effect of flame retardant concentration on penetration.
modified asphalt binders show the most dramatic change
Fig. 3 shows that the low-temperature ductility of the flame-
among the flame retardants. Experimental results indicate that
resistant modified asphalt binders decreases gradually with the
the effect of EBPED on softening point is different from
increase in flame-resistant concentration besides simple
antimony trioxide and zinc borate.
EBPED modified asphalt binder. Aluminium trihydroxide
As flame retardant concentration increases, the penetration
shows greater effect on ductility than other flame retardants.
values of flame-resistant asphalts exhibit monotonously reduce,
EBPED modified asphalt binder has a similar ductility of more
shown in Fig. 2. The reason may be that asphalt binder
than 200 cm compared with unmodified asphalt binder. Single
becomes hardening because flame retardant powders absorb
inorganic flame retardants have great effect on ductility, but the
the oily composition of asphalt. Comparing with experimental
influences tend to be stable with increasing flame retardant
results, the effect of EBPED is larger than other simple flame
retardants, and the penetration values decrease from 65.1 to concentration. The ductility decreases sharply when inorganic
47.6 dmm when EBPED content ranges of 1–6%, exhibiting an flame retardant concentration is less than 3 wt%, and decreases
obvious reducing tendency. Other simple modified asphalt gently when inorganic flame retardant concentration is more
binders impair penetration slightly, and penetration change is than 3 wt%. The change trends of the ductility for EBPED/
less than 10 dmm within the same range of flame retardant. The antimony trioxide and EBPED/ZB/antimony trioxide modified
addition of EBPED is expected to further decrease the asphalt binders are located between the one of EBPED
penetration values of zinc borate or antimony trioxide simple modified binder and the one of inorganic flame retardant
modified binders at the same total contents. But the mixed modified binder. Hence, flame-resistant modified asphalt
modifies system do not have advantage of EBPED simple binder with suitable ductility can be obtained by mixed flame
modified binder, which demonstrate the great effect of EBPED retardants modified.
on penetration again. Table 1 lists the variation in related properties of different
modified asphalt by flame retardants after short-term aging

Fig. 1. Effect of flame retardant concentration on softening point. Fig. 3. Effect of flame retardant concentration on ductility.
 S. Wu et al. / Fuel 85 (2006) 1298–1304 1301

Table 1 modified asphalts, the maximal differences for the zinc borate
Effect of short-term aging on related properties of flame-resistant asphalt modified asphalts is 2.2 8C when the zinc borate concentration
binders
is 5 wt%. The differences for other flame retardant modified
Flame retardant concen- Mass loss PRP DT AI asphalts are less than 2.2 8C, which indicate the well storage
tration (%) (%) (8C) stability of sole flame retardant modified asphalts.
5% EBPED 0.022 83.1 4.8 0.0075 The difference of softening points for the EBPED/ antimony
2.5% Zinc borate 0.107 86.1 4.7 0.0179 trioxide (3:1) modified asphalt binders is 3.8 8C when the
2.5% Antimony trioxide 0.188 85.9 4.7 0.0086
concentration is 7 wt%, shown in Fig. 5. The flame retardants
5% Aluminium trihydroxide 0.116 81.7 4.5 0.0057
6% EBPED: Zinc borate: 0.034 83.9 4.9 0.0118 show the difference in the solubility parameter and density to
Antimony trioxideZ3:1:1 asphalt. Granules of flame retardants dispersed in asphalt are
usually accumulated and subside to the bottom of the asphalt at
a high temperature and static state. The density of EBPED is
compared with unaging binders. The mass was lost for all
larger than other flame retardants, the granules of EBPED
flame-resistant asphalt binders after TFOT and the mass loss subside to the bottom at elevated temperatures since the gravity
ranges from 0.02 to 0.2% compared with unaging binders.
effect. Because EBPED is organic material, it can be dissolved
Modified asphalt containing 5 wt% EBPED has the least mass
in asphalt partially. Dissolution decreases the concentration of
loss, but the one containing 2.5 wt% antimony trioxide has the
dissimilar phase, which is helpful to reduce the phase
largest mass loss among all the modified binders. The percent
separation. Antimony trioxide and zinc borate are mineral
retained penetration (PRP) of all flame-resistant modifies
materials, which are indiscerptible with asphalt. Therefore,
asphalt binders are greater than 75%. It may be that the aging
storage stability was affected by the nature and concentration
resistance of asphalt binders was improved when flame
of flame retardants. Asphalt binders modified by the flame
retardants existed. For example, The PRP of 5 wt% EBPED, retardants with greater density are expected to take place the
2.5 wt% zinc borate, 2.5 wt% antimony trioxide, 5 wt%
worse phase separation and the ones modified by flame
aluminium trihydroxide and 6% EBPED/ZB/Antimony tri-
retardants with mutual solubility may have a slight phase
oxide(3:1:1) modified asphalt binder is 83.1, 86.1, 85.9, 81.7,
separation. Experimental results of storage stability of various
and 83.9%, respectively. The increments in softening point
flame-resistant asphalt binders indicate that asphalt binders
show almost similar results, which indicate that the short-term
with various flame retardant concentration show different
aging has not a different effect on softening point.
change trends, which provides a feasible way to prepare a
3.2. Storage stability suitable asphalt binder with qualified storage stability under the
function of solubility and density interaction.
The flame-resistant asphalt binders are multi-phase systems,
so possible phase separation and chemic reaction under static 3.3. Rotational viscosity
conditions should be evaluated. The effect of flame retardant
concentration on storage stability of the flame-resistant asphalt Most modified asphalt binders are non-Newtonian fluids at
is shown in Figs. 4 and 5. Compared with the large differences mixing and compacting temperature range in situ currently.
in the top and bottom sections of the sole flame retardant The effect of viscosity on asphalt binder’s workability is very

Fig. 4. Effect of sole flame retardant concentration on storage stability.

1302 S. Wu et al. / Fuel 85 (2006) 1298–1304
Fig. 5. Effect of mixed flame-retardant concentration on storage stability.
important in selecting proper mixing and compacting tem-
peratures. Figs. 6 and 7 show the effect of type and
concentration of flame retardants on rotational viscosity.
Fig. 6 shows that the increase in asphalt viscosity is not
directly proportional to the flame retardant concentration.
Among all the flame retardants, EBPED has a least effect on
asphalt viscosity, but antimony trioxide has a greatest one. A
sudden change in viscosity is observed when the flame
retardant concentration exceeds 2 wt%, which is resulted in
the decrease of light oil constituents imbibed by certain
molecules. The EBPED modified asphalt viscosity is pro-
portional to the amount of EBPED added, which illuminate that
certain molecular interactions may exist among organic
molecules and light oil constituents in asphalt through swelling
and/or solution partly.
The viscosity of the flame-resistant asphalts is higher than
that of the original asphalt, as shown in Fig. 7. There are large
Fig. 6. Effect of flame retardant concentration on viscosity at 135 8C.
difference among various flame retardants when temperature
less than 135 8C. The viscosity of asphalt binder containing
6.0% antimony trioxide is over two times higher than that of
the original asphalt at 110 8C, and about 1 time higher at
120 8C. The viscosity at 135 8C must not be greater than 3 Pa.s
according to Superpave binder specification limits. Whereas,
test results show that the viscosity of antimony trioxide and
EBPED modified asphalt binder is 0.81 and 0.5 Pa.s,
respectively, which indicate the viscosity of modified asphalt
binders at 135 8C can meet the requirement of the related
construction temperature.
3.4. Thermal analysis
Fig. 8 illustrates the results of DSC test of original asphalt
and two samples containing different concentrations of
Fig. 7. Viscosity–temperature curve of total 6 wt% flame retardant.
 S. Wu et al. / Fuel 85 (2006) 1298–1304
Fig. 8. DSC tests of original and flame-resistant asphalt binders.
Fig. 9. Effect of flame retardants and concentrations on flame retardancy.
EBPED, antimony trioxide and Zinc borate flame retardants.
Asphalt is complex mixture of high molecular weight
hydrocarbon molecules, so it exhibits a great number of
exothermic peaks during DSC test, which indicate that plenty
of ingredient transforms occur in this temperature range. Small
molecules transform at lower temperature, but large molecules
transform at higher temperature. The exothermic peak of wax
generally exhibits at the temperature range of 30–40 8C.
The thermal behaviour of the two samples is essentially
dependent on temperature and flame retardant concentration.
Zinc borate starts to give off vapour and EBPED decomposes
of HBr, which lower temperature. At the same time, oxygen
concentration is diluted when the temperature increases. The
decomposition and vapour leads to lower temperature and the
Table 2
The regulations of Japan JISK 7201
Classification Nonflame-1 Nonflame-2
LOI LOIO30 27!LOI!30
1303
exothermic peaks of DSC curves decline and the DSC curves
are lower than original asphalt’s before 425 8C. The DSC curve
of original asphalt appears a wide exothermic peaks at
temperature range of 385–425 8C, which is the mostly
decomposition temperature of original asphalt. However, the
flame retardants postpone the appearance of exothermic peak
and reduce the peak value. The main absorbing peak appears
when temperature high than 450 8C, which indicates the flame
retardants act. Therefore, the flame retardancy of asphalt was
improved by the addition of flame retardants and the
mechanism of flame retardancy involves the combined function
of gaseous liquid and solid mechanism. The exothermic peak
on the DSC curve was postponed towards high-temperature
region, which delay fire failure, thus buys time for extermina-
tion of fire.
3.5. Flame retardancy
Fig. 9 shows the effect of flame retardant and concentrations
on flame retardancy and indicates that adding flame retardant
increases LOI, especially the mixed flame retardants added. As
a result, the slope of LOI master curve decreases with
increasing concentration, meaning that flame retardant makes
the asphalt better flame retardancy. For the sole flame
retardant, the change in LOI is relatively small with increasing
concentration. In accordance with Japan JISK 7201 regulations
listed in Table 2, the flame-resistant asphalt binders were
classified into five categories through the LOI. Experimental
analysis of LOI indicates that variations of flame retardant
concentrations within the selected ranges have the most
significant effect in increasing the flame retardancy of asphalt
binders. The original asphalt is classified as Nonflame-5.
However, it became Nonflame-4 when a small amount of flame
retardant is added. If 6 wt% (EBPED: antimony trioxide: zinc
borateZ3:1:1) mixed flame retardants are added into asphalt,
an asphalt binder of Nonflame-3 is obtained. Therefore, the
mixed flame retardants has the more significant effect on
improving the flame retardancy than the sole flame retardant at
the same concentration, which implies superior flame
retardancy can obtain by adding mixed flame retardants.
Fig. 9 shows that increasing zinc borate or antimony trioxide
concentrations increase slightly in LOI. The EBPED show
better flame retardancy than zinc borate or antimony trioxide,
but LOI improvement is not markable as anticipated. Whereas,
mixed flame retardants of EBPED and antimony trioxide have
appreciable advantages over the related sole flame retardant at
the same concentration. The higher LOI may be attributed to
the synergistic effect between EBPED and antimony trioxide.
Thus, the results mentioned above conclude that the synergistic
effect of mixed flame retardants is a best means to improve
Nonflame-3 Nonflame-4 Nonflame-5
24!LOI!27 21!LOI!24 LOI!21
1304 S. Wu et al. / Fuel 85 (2006) 1298–1304

flame retardancy of asphalt and reduce the effect on other Acknowledgements

related properties of asphalt binder.
Support for this work by the Department of Transportation
4. Conclusions in Hubei Province, China and Headquarters of Hurong-Xi
Expressway in Hubei Province is greatly appreciated.
Asphalt has no flame retardancy, but the incorporation of
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