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Materials and Structures (2015) 48:205216

DOI 10.1617/s11527-013-0177-3

ORIGINAL ARTICLE

Sulfur extended heavy oil fly ash and cement waste asphalt
mastic for roofing and waterproofing
M. A. Dalhat H. I. Al-Abdul Wahhab

Received: 20 October 2012 / Accepted: 31 August 2013 / Published online: 7 September 2013
RILEM 2013

Abstract Waste materials recycling has been the


logical and widely accepted means of conserving the
diminishing global natural resources. This comes as a
result of increased scarcity of raw industrial materials,
coupled with environmental hazard of most of the
waste products. In this paper, the effect of different
waste material fillers, namely heavy oil fly ash
(HOFA), coal fly ash, limestone dust, and cement kiln
dust, and sulfur on the physical properties and
performance of roofing and waterproofing asphalt
has been examined. Conventional asphalt consistency
tests in addition to a new bond strength test were
conducted on the modified asphalt mastic. The results
were analyzed statistically and assessed in accordance
with ASTM D 332 and ASTM D 449 specifications.
HOFA proved to be a superior filler additive compared
to the other three additives. The sulfur mixes were
found to be short on flash point values, but in spite of
this, results show a promising potential alternative and
cost effective material composite having the least
amount of asphalt content.
Keywords Roofing asphalt  Mastic asphalt 
Heavy oil fly ash  Coal fly ash  Bond strength

M. A. Dalhat (&)  H. I. Al-Abdul Wahhab


Civil & Environmental Engineering Department,
KFUPM, Dhahran 31261, Saudi Arabia
e-mail: madab@kfupm.edu.sa

1 Introduction
Eighty-five percent of the global demand for asphalt
(over 100 million metric tons per year and growing) is
generated from road construction [1]. Due to the
limited asphalt supply, the remaining 15 % of asphalt
demand which comes mainly from waterproofing
applications is facing a fierce competition that can
only be lessened through an alternative material
supplement, a move that will provide means of waste
recycling, which in turn will help conserve our scarce
natural material resources and promote green construction. In Saudi Arabia, about 10,000 tons of sulfur
is produced from crude refining on daily basis [2].
More than 12 mega tons of cement kiln dust (CKD)
and limestone dust (LMD) combined is yielded yearly,
while 340,000 m3 of heavy oil fly ash (HOFA) waste is
generated annually.
Traditionally, asphalt-based roofing and waterproofing products were made from air blown asphalt,
but as roofing chemistry became more sophisticated,
various formulations with different viscosity ranges,
physical and mechanical properties (for horizontal and
vertical applications) were developed for specific uses
from a regular asphalt/bitumen by chemical and
mineralogical contents modification, such as pourable
sealers (pitch pocket mastics), elastomeric sealants
(mastics for high movement joints and terminations),
etc. This is due to the fact that the improvements
achieved on the bituminous materials durability and
extensibility (especially at lower temperatures) by

206

adding polymers, result in modified material with


superior physical properties that surpass any other
alternative material for the same cost.
The roofing asphalt polymer modification is well
explored, understood and lots of works were published
on the subject [38]. Apart from polymer, another
major additive which also dictates the final performance of this waterproofing mastic asphalt, is the
mineral filler. Studies have been conducted to investigate the effect of different mineral fillers on certain
properties of the asphalt binder [911], but nearly all
of these works were directed towards the behavior and
durability of asphalt concrete pavement (AC), and not
on roofing or waterproofing applications, besides the
monopoly in the selection of mineral filler type for
roofing purposes [12], which is LMD. The possibility
of an alternative filler additive which is better or
equivalent to limestone in terms of serviceability
performance of waterproofing asphalt has not been
explored so far.
Sulfur extended asphalt (SEA) has been used in
asphalt concrete (AC) due to its improved rutting
resistance and storage stability [13, 14, 15]. Numerous
researches proved that up to 50 % of the asphalt mastic
constituent in AC can be substituted by sulfur without
much affecting the AC engineering properties in terms
of performance and durability [16]. However, these
results cannot be relied upon when it comes to roofing/
waterproofing applications. SEA was also used for
roofing applications [17], but with sulfur just as a mere
extender without fire safety hazard assessment such as
the specification test for flash and fire point (ASTM D
92) or for asphalt roof cement (ASTM D 2822). The
reactions between sulfur and asphalt have been
investigated [18], it was shown that sulfur reacted in
two different ways. At higher temperatures (240 C),
it dehydrogenated asphalt; at lower temperatures
(140 C), it combined with asphalt with the inclusion
of sulfur, giving a more ductile material. The duration
of asphalt/sulfur mixing was not reported; only up to
15 % of sulfur was used in the study and ductility test
was not conducted at the ASTM specified room
temperature (25 C).
There seem to be an environmental concern when it
comes to the use of SEA, due to its emission of
harmful gases like hydrogen sulfide (H2S) and sulfur
oxides (SO2) at high temperature. The emission of
these gases is governed primarily not by the amount of
sulfur in the asphalt, but mainly by the temperature of

Materials and Structures (2015) 48:205216

handling and amount of reacted sulfur [19, 18].


General safety precaution is to minimize the operation
temperature, so as to contain the concentrations of the
emitted fumes within standard allowable limit [16].
And to restrict workers time exposure through hourly
shift. The use of degassed sulfur has also been
reported [16]. Prolong storage time (beyond mostly
4 h) in hot state, is strongly discouraged. These
conclusions were drawn from researches conducted
on asphalt concrete containing binder modified by up
to 50 % sulfur. Results also shows sulfur asphalt to
have minimal spills contamination and little impact on
surface runoff water [20]. In a similar study, the air
quality around sulfur asphalt plant and in situ were
monitored in terms of H2S and SO2-concentration
[21]. The H2S and SO2-level were found to averagely
range below the standard limit value (5 ppm).
The famous asphalt physical tests such as ductility
test (ASTM D 113), penetration test (ASTM D 5),
softening point (SP) test (ASTM D 36), and flash and
fire point test (ASTM D 92) formed the basis for
general specifications in roofing asphalt cements,
asphalt for waterproofing and damp proofing applications and so on [22, 23]. There is lack of adequate
standard test to appropriately assess and characterize
the asphalt mastic on its own at semi-finished product
level for this application [24]. In this study, a new
mastic bond strength test has been devised for
assessing its performance.
The influence of sulfur, HOFA, CKD, LMD and
coal fly ash (CFA) on the physical properties of
asphalt, namely SP, ductility, penetration, flash point
and viscosity have been studied. Further, their effect
on its bond strength was also examined.

2 Materials and methodology


2.1 Materials
The asphalt used in this study is the only local
available grade, and it was obtained from Riyadh
refinery. It has the physical properties as shown in
Table 1.
Cement kiln dust and LMD, which are byproducts
of limestone quarrying and cement manufacturing,
were obtained from a local road construction company. Sulfur was obtained locally from Saudi Aramco
Oil Company. HOFA was collected from Rabiq

Materials and Structures (2015) 48:205216

207

2.2 Sample preparation

Table 1 Asphalt physical properties


Property

Magnitude

Ductility (cm)

150?

Penetration (dmm)

67.2

Softening point (C)


Flash point (C)

52
342

Viscosity (cP)

575

thermal power station located in the western coast of


the Kingdom of Saudi Arabia, which is the Red Sea
coast. CFA which is not popular in this part of the
globe due to the absence of its material source (coal),
was obtained from Saudi Ready Mix Concrete
Company.
Heavy oil fly ash (HOFA), a by-product of fuel
combustion process, includes diesel and cracked fuel.
It is typically a black powder type of waste material
containing mainly carbon, generated from thermal
electric power plants. Typical chemical constituent
analysis of HOFA is shown in Table 2. The amount of
each element can vary depending on the source of
HOFA [25].
The reuse of HOFA for a wide variety of
purposes can be seen from the recent and old
literature. It has been studied as an adsorption
medium for CO2, the so called carbon capture. Its
potential as a filler reinforcement in light density
polyethylene (LDPE) polymer composite has also
been reported [26]. Results show an improvement in
rheological properties of the modified LDPE. Furthermore, the patented means of improving the
performance of an asphalt binder and concrete with
the use of HOFA has been disclosed [25]. HOFAasphalt mixes proved to be within the asphalt
performance grade limits with potential improvement in durability and strength.

Table 2 Elemental composition of HOFA


Element

Weight (%)

Carbon

92.5

Magnesium

0.79

Silicon

0.09

Sulfur

5.80

Vanadium

0.61

2.2.1 Sulfur-filler blends


Fillers were placed in the oven for 24 h at 100105 C
prior to mixing in order to eliminate moisture. 800 g of
neat asphalt was poured into a 1,000 ml mixing can;
the can was then placed in an oil bathe at 140145 C
[18]. The asphalt is continuously stirred with the aid of
a high speed shear mixer (2500 rpm) until the
temperature equilibrium between the bathe and the
container has been established. Appropriate amount of
sulfur (10, 20 and 30 %) by weight of the 800 g
asphalt was introduced into the mix, and the stirring
will continue for 10 min. Afterwards, the final mix
was poured into four new mixing cans and stored
temporarily for not more than 30 min inside the oven
at 145 C. The four blends were then mixed in the
same manner as previously mentioned with an appropriate filler content (10, 15, 20 and 25 %) for 5 min,
the test samples were cast immediately for each blend
to avoid a prolonged storage additive settlement or
separation. The generalized sulfur-filler mastic formulation is given in Table 3.

2.2.2 SBS-sulfur-filler blends


Finely grounded SBS (styrenebutadienestyrene)
powder having high specific surface area was used.
420 g of liquid asphalt was mixed with 5 or 10 % of
the SBS manually with a spatula spoon to ensure
uniform distribution of the polymer particles. The can
was then sealed with the aid of aluminum foil and
paper tape, and placed inside the oven for approximately 2 h at 160 C for the SBS particulate to swell
and soften. This blend was then placed in an oil bathe
at 190200 C and blended with high shear mixer at
2,500 rpm for 20 min. The resulting blend was further
divided into two new containers for final mixing with
the mineral fillers. The mineral addition was also done
at the same temperature and speed for 5 min. The
sealed storing helps eliminate the effect of asphalt
oxidation. If the blend design contains sulfur, the
appropriate amount of sulfur was added and the
mixing was carried out for 2 min maximum. The blend
was then put into an oven for at least 20 min at a
temperature above 170 C for the vulcanization process to complete before the test samples were casted.

Note that, the sulfur composition is by asphalt weight, and the filler composition is by asphalt weight in the case of the plain asphalt or by SEA weight in the case of sulfur
asphalt

140 g_asphalt ?
42 g_sulfur ? 45.5 g_filler
140 g_asphalt ?
42 g_sulfur ? 36.4 g _ filler
140 g_asphalt ?
42 g_sulfur ? 0 g_filler
30 % Sulfur

140 g_asphalt ?
42 g_sulfur ? 18.2 g_filler

140 g_asphalt ?
42 g_sulfur ? 27.3 g_filler

160 g_asphalt ?
32 g_sulfur ? 48.0 g_filler
160 g_asphalt ?
32 g_sulfur ? 38.4 g_filler
160 g_asphalt ?
32 g_sulfur ? 0 g_filler
20 % Sulfur

160 g_asphalt ?
32 g_sulfur ? 19.2 g_filler

160 g_asphalt ?
32 g_sulfur ? 28.8 g_filler

180 g_asphalt ?
18 g_sulfur ? 49.5 g_filler
180 g_asphalt ?
18 g_sulfur ? 39.6 g_filler
180 g_asphalt ?
18 g_sulfur ? 0 g_filler
10 % Sulfur

180 g_asphalt ?
18 g_sulfur ?
19.8 g_filler

180 g_asphalt ?
18 g_sulfur ? 29.7 g_filler

200 g_asphalt ?
50 g_filler
200 g_asphalt ?
40 g_filler
200 g_asphalt ?
30 g_filler
200 g_asphalt ?
20 g_filler
Plain asphalt
0 % Sulfur

10 %
0%

% By weight of filler
Binder type

Generalized mastic formulationa

Table 3 Sulfur-filler mastic experimental design

15 %

25 %

Materials and Structures (2015) 48:205216

20 %

208

2.3 Properties measurement


Conventional asphalt physical tests such as ductility
test (ASTM D 113), penetration test (ASTM D 5), SP
test (ASTM D 36), flash and fire point test (ASTM D
92) were first carried out. And an additional viscosity
test (ASTM D 4402), using Brookfield DV II?
rotational viscometer with RV4 cylindrical spindle
of multiplying constant SMC 20, was conducted on
the samples. Then, selective blends were assessed by a
bond strength test, which was developed in this study
to assess the bond strength of asphalt mastics to
smooth aluminum surfaces.
2.4 Tensile bond strength test
The bond strength test was devised to measure the
asphalt mastic ability to resist tensile force and to
transfer a sizable amount of force between two bonded
surfaces. It is also an indicator of the maximum bond
strength the mastic can surmount when subjected to
tension. The test involves loading a 30 mm by 20 mm
by 6 mm prepared sample of the asphalt mastic in
tension at a rate of 1.3 mm/min at 25 C [27]. The load
magnitude and its corresponding deformation are
measured in the process. The tensile strength is
reported as the maximum stress recorded, which is
obtained by dividing the highest load carried by the
sample before it fails, by the plate area.
The current active specification test method for
asphalt base expansion joint filler (ASTM D 545-08:
standard test methods for preformed expansion joint
filler for concrete construction) has prescribed the
means to check and measure the suitability of joint
sealant performance and durability through various
tests which include failure due to compression test.
However, it failed to include tensile failure test despite
the fact that joint openings are bound to widen during
winter as they are likely to narrow in summer season,
since the concrete does not only expand but also
contract. Another major common defect exhibited by
asphalt waterproofing membrane on flat roofing system is the formation of blisters [28]. Blisters propagate
more easily after the initial bond loss between the
membrane and the roofing deck if the membrane is
lacking in tensile strength. A delaminated membrane
having a low tensile bond strength (TBS) will certainly
swell and bulge at the slightest given opportunity, and
as a result facilitates the whole failure process.

Materials and Structures (2015) 48:205216

209

asphalt mastic film

Fig. 1 Tensile bond


strength test setup

top and bottom plates

uniform stress

20mm

2.4.1 Apparatus
The apparatus consists of two 30 mm by 20 mm by
6 mm plates, a mechanism which holds and stretches
the sample while the load is applied as shown in Fig. 1,
and a hydraulic or screwed-up device.
A sample grip having a wedged-like edge slot
matching the size and shape of the plate is fixed to the
load mechanism main frame upper block with the aid
of a short steel rod that is supplemented with spring
bearing to help eliminate any unnecessary compressive force while the sample is being inserted. The
upper part of the mechanism rests on a bearing or
spring suspension system which eliminates any additional load on the tested sample due to the self-weight
of the upper frame.

disturbance. Then, the sample was put in a 25 C


water bathe for at least 90 min before testing.
2.5 Statistical analysis of results
A two-way analysis of variance (ANOVA) was
conducted on the physical test results obtained with
the additives used as effects/factors, using Minitab 16
statistical software. This is to ascertain the relative
effectiveness of the fillers within the extenders (sulfur)
and also the extenders level of influence on the asphalt
properties. But before ANOVA was selected for the
analysis, model adequacy check was performed on the
data. Tests such as equality of variance test and
normality check test were carried out to ensure the
relevance and appropriateness of the selected test
method.

2.4.2 Sample casting


The two plates were spaced 6 mm apart and fixed in
position with the aid of a holder; three sides of the
arrangement were wrapped with a non-sticking paper.
The plates and mastic were heated to a workable state
capable of filling the 6 mm 9 20 mm 9 30 mm
space without voids and also to promote sticking to
the plate wall with full strength. The material was
allowed to cool sufficiently before unwrapping it, for
at least 15 min. When necessary, the sample was put in
the freezer after 30 min for 5 min to enable the smooth
removal of the non-stick paper without sample

3 Results and discussion


3.1 Softening point (SP)
The SP is defined as the temperature at which a
bitumen sample can no longer support the weight of a
3.5-g steel ball. It is a measure of the temperature at
which the material will begin to flow (or soften).
Generally, the SP is negatively affected with more
sulfur additive and increases with increment in HOFA
content as shown in Fig. 2. In pure HOFA-asphalt

210

Materials and Structures (2015) 48:205216


70
CKD - 0% Sulfur
CKD - 10% sulfur
CKD - 20% sulfur
CKD - 30% sulfur
LMD - 0% Sulfur
LMD - 10% Sulfur
LMD - 20% Sulfur
LMD - 30% Sulfur
HOFA - 0% Sulfur
HOFA - 10% Sulfur
HOFA - 20% Sulfur
HOFA - 30% Sulfur
CFA - 0% Sulfur

Softening Point, oC

65

60

55

50

45

40
0%

10%

15%

20%

25%

Fillers (HOFA, CKD, LMD & CFA)


Fig. 2 Softening point versus fillers (HOFA, CKD, LMD and CFA)

blends, an insignificant change can be observed within


1020 % HOFA content, but a drastic additional rise
by about 7 C in SP was recorded for the mix
containing 25 % HOFA. The initial 10 % HOFA
resulted to almost 18 % rise. On the other hand,
addition of sulfur to the neat bitumen does not seem to
change the SP within 010 % range, but at higher
doses (2030 %) the SP seems to diminish by
approximately 13 %. Combining both sulfur and
HOFA seems to have an overall destructive resultant,
sulfur will lower the SP while HOFA will tend to push
it up. An equilibrium value that is in-between pure
Sulfur/HOFA blend will always be the resulting SP
depending on the relative proportion of these additives, but will be closer to the HOFA-asphalt blend
value for equal weight combination.
An increase in SP was also observed with higher
LMD content, as shown in Fig. 2, but unlike HOFA,
LMD has little influence on this parameter. A 7 % rise
was recorded for the initial 10 % composition, and
25 % was able to annul the dwindling effect of 30 %
sulfur on the SP. In contrast to HOFA and LMD, the
effect of CKD on SP can be observed to be uniform for
CKD-only blends, as shown in Fig. 2. An average
increment of 1 C can be seen for every 5 % additional
CKD contents. 15 % was enough to nullify the
lessening effect of sulfur on the SP. However, 10 %
sulfur curve proved to be the softest combination,

which might be due to the relatively lesser amount of


filler grains (sulfur and CKD combined). The CFA has
certain positive effect on the SP compared to LMD and
CKD but far below the HOFA level, as can be seen
from the CFA-0 % sulfur in Fig. 2.
3.2 Penetration
This test measures the penetration of a standard needle
into the asphalt binder sample under 100 g weight in
5 s at 25 C. It is a measure of the material hardness at
room temperature.
The manner in which the asphalt penetration is
affected by sulfur additive depends on the amount of
sulfur used to replace the asphalt component. As
reported from previous work [29], at ranges between 0
and 10 % sulfur the penetration seems to be declining
with more sulfur, while beyond this interval it can be
seen to be rising until it is higher than that of neat
asphalt at 30 % sulfur, as shown in Fig. 3. As opposed
to the other fillers, a continuous decline in penetration
with more HOFA is evident for all HOFA mixes,
which can be related to the relative larger surface area
and absorption capacity. The effectiveness of HOFA
in cutting the penetration value of the asphalt has been
attenuated by sulfur additive in the Sulfur-HOFA
blends; the 20 and 30 % sulfur curves exhibited almost
similar penetration.

Materials and Structures (2015) 48:205216

211

100

CKD - 0% Sulfur
CKD - 10% Sulfur
CKD - 20% Sulfur
CKD - 30% Sulfur
LMD - 0% Sulfur
LMD - 10% Sulfur
LMD - 20% Sulfur
LMD - 30% Sulfur
HOFA - 0% Sulfur
HOFA - 10% Sulfur
HOFA - 20% Sulfur
HOFA - 30% Sulfur
CFA - 0% Sulfur

Penetration, dmm @25 C

80

60

40

20

0
0%

10%

15%

20%

25%

Fillers (HOFA, CKD, LMD & CFA)


Fig. 3 Penetration versus fillers (HOFA, CKD, LMD and CFA)

An abnormal rise in penetration value with increasing CKD/LMD content can be observed for 20 and
30 % sulfur curves, as shown in Fig. 3. Instead of
declining with more filler content as usual, the
penetration keeps rising up to certain filler content
before it begins to drop. The possible explanation to
this different characteristic could be due to the
relatively higher particle size of CKD and LMD
compared to HOFA. This will result to uneven and
sparsely distributed filler-grains which produce less
strong CKD-asphalt-sulfur monolith having weaker
asphalt-sulfur three dimensional spots at lower CKD/
LMD content. When the penetration needle is
released, it passes through these weak spots and easily
pushes downward any CKD/LMD particle blocking its
path. So, even when the CKD/LMD quantity
increases, the result is a more weaker adhesion of
the asphalt-sulfur fluid to the more numerous CKD/
LMD grains. As these fines are increased further, their
downward displacement by the needle tends to slow
down, thus resulting in relatively lesser penetration
value (25 % CKD). At higher sulfur content (30 %
sulfur), the 3-dimensional matrix is more stably
compact due to the presence of surplus unreacted
sulfur crystals [18]. This results in a continuous
decrease in downward and lateral displacement of the
CKD grains as they are now situated in a highly filled
asphalt matrix. The 0 % sulfur-CFA blends exhibited

penetration value similar to those of LMD and CKD,


but higher than that of the HOFA mastic, as can be
seen from Fig. 3.
3.3 Ductility
Ductility is a measure of the ease with which the
material can be deformed plastically at room temperature. Ductility test measures asphalt mastic ductility
by stretching a standard-sized briquette of asphalt
sample to its breaking point at 25 C.
Addition of sulfur to the asphalt resulted in low
ductile composite. A loss of more than 50 % in
ductility can be observed from Fig. 4 at 20 % sulfur
content. More significant reduction is evident with the
addition of HOFA to the neat asphalt; initial 10 %
eliminated more than 85 % of the fresh asphalt ductile
property. Even though both sulfur and HOFA negatively affect the ductility individually, a material with
relatively higher ductility than purely HOFA-blend is
obtained when they are combined.
Ductility also decreased with more LMD, but not as
considerably as in the case of HOFA. A drop of about
35 % can be seen at 10 % LMD content, as shown in
Fig. 4. When combined together with sulfur, the
resultant ductility always seems to be lower than both
results obtained with LMD and sulfur when used
individually alone. CKD-asphalt blend shows lower

212

Materials and Structures (2015) 48:205216


160
140

CKD - 0% Sulfur
CKD - 10% Sulfur
CKD - 20% Sulfur
CKD - 30% Sulfur
LMD - 0% Sulfur
LMD - 10% Sulfur
LMD - 20% Sulfur
LMD - 30% Sulfur
HOFA 0% Sulfur
HOFA 10% Sulfur
HOFA 20% Sulfur
HOFA 30% Sulfur
CFA - 0% Sulfur

Ductility, cm @ 25 C

120
100
80
60
40
20
0

0%

10%

15%

20%

25%

Filler (HOFA, CKD, LMD & CFA)

3.4 Viscosity
The addition of sulfur to neat asphalt caused a gradual
drop in its viscosity. Initially (at 10 %), the effect was
minimal with just a decrease of about 2 % since most
of the sulfur elements have reacted with the naphthenic component of the asphalt to form polysulfurized aromatics [18], followed by a significant drop of
more than 40 % at 20 % sulfur (Fig. 5) due to the
presence of extra unreacted sulfur colloid. On the
other hand, HOFA shows a tremendous thickening
ability, which could be attributed to its ability to
absorb the oily constituent of the asphalt, and in turn
resulted to a higher interlayer friction. 10 % HOFA led
to about 200 % rise in viscosity. Mixing sulfur with
the HOFA-blend brought the viscosity close to the
original value, especially within 2030 % sulfur and
1015 % HOFA range combinations.

CKD - 0% Sulfur
CKD - 10% Sulfur
CKD - 20% Sulfur
CKD - 30% Sulfur
LMD - 0% Sulfur
LMD - 10% Sulfur
LMD - 20% Sulfur
LMD - 30% Sulfur
HOFA - 0% Sulfur
HOFA - 10% Sulfur
HOFA - 20% Sulfur
HOFA - 30% Sulfur
CFA - 0% Sulfur

5000

4000

ductile behavior compared to their LMD blend


counterparts. A 67 % loss in ductility was recorded
as compared to 35 % for LMD-asphalt mix. But as in
sulfur-limestone blend, the resulting ductility of
combined sulfur-CKD is lower than that of either
CKD-alone or sulfur-only blend. Pure CFA mastics
possess ductility that is even higher than the HOFASulfur mastics, but lower than all LMD blends, as can
be seen from Fig. 4.

Viscosity, (cP) @ 135 C, 20 rpm

Fig. 4 Ductility versus fillers (HOFA, CKD, LMD and CFA)

3000

2000

1000

0
0%

10%

15%

20%

25%

Fillers (HOFA, CKD, LMD & CFA)

Fig. 5 Viscosity versus fillers (HOFA, CKD, LMD and CFA)

The LMD does not seem to change the viscosity


significantly but an increase of 300 cP could be
noticed for the first 10 % LMD, as can be seen from
Fig. 5. Afterwards, there seems to be no change up to
20 % LMD content. Adding sulfur caused the viscosity to go down below the normal asphalt viscosity; this
was observed for all sulfur containing LMD-asphalt
blend. The CKD blends more or less behaved in a
similar manner as the LMD mixes. The CKD mastics
containing sulfur possess lower viscosity than the neat
bitumen; the viscosity appreciates for CKD-only
blends but not considerably as in HOFA. The CFAonly mastics show viscosity equal or just a little above

Materials and Structures (2015) 48:205216

213

the CKD and LMD-only mastics, which are all far


below that of the HOFA-only blends, as shown in
Fig. 5.
2

Bond strength (kN/m )

1000

3.5 Flash point (FP)


Flash point (FP) is a measure of the minimum
temperature at which the material will ignite. It serves
as an indicator for fire risk assessment (safety when
handling and in service).
The mineral fillers and HOFA have little or no
effect on the flash point. The maximum difference
between neat asphalt value and the highest filler
content (25 %) is not more than 15 C, which is very
little compared to the original 340 C. On the contrary,
the sulfur results in more than 100 C decrease for just
10 % composition. This is a result of the release of
flammable gases like hydrogen sulfide by the sulfur
modified asphalt at temperature above 149 C [16].
Beyond 10 % sulfur content, the rate of decline ceases
to about 5 C for every 10 % more sulfur, which is
virtually insignificant, as can be seen from Fig. 6.
Similar trend was observed for the LMD-Sulfur
mixes as in the HOFA-Sulfur blend. The horizontal
change in flash point due to filler increase tends to be a
little more pronounced with CKD as compared to the
other two additives (HOFA and LMD), especially for
the CKD-only blends, as can be seen from Fig. 6. This
might be due to the diverse additive composition such

100

Bond strength vs. Sulfur


Bond strength vs. SBS
Bond stregth vs. 5%Sulfur with
varying SBS

10
0%

3%

5%

8%

10%

as sulphospurite and spurite resulting from the cement


manufacturing. The CFA-only blends show similar FP
result as the HOFA-only mastics.
3.6 Tensile bond strength (TBS)
The bond strength (TBS) slightly increased with more
sulfur initially, and then starts to decline at higher
content as shown in Fig. 7. At lower percent composition of up to 20 %, most of the sulfur additives got
attached to naphthenic constituent of the asphalt,
forming extra asphaltene in the process [18], which is

340

CKD - 0% Sulfur
CKD - 10% Sulfur
CKD - 20% Sulfur
CKD - 30% Sulfur
LMD - 0% Sulfur
LMD - 10% - Sulfur
LMD - 20% Sulfur
LMD - 30% Sulfur
HOFA - 0% Sulfur
HOFA - 10% Sulfur
HOFA - 20% Sulfur
HOFA - 30% Sulfur
CFA - 0% Sulfur

320

Flash Point, C

300
280
260
240
220
200
180
160
10%

15%

20%

Fillers (HOHA, CKD, LMD &CFA)


Fig. 6 Flash point versus fillers (HOFA, CKD, LMD and CFA)

30%

Fig. 7 Bond strength versus SBS, sulfur and SBS-sulfur mastic

360

0%

20%

SBS/sulfur

25%

214

Materials and Structures (2015) 48:205216


600

Bond Strength, kN/m

500

400

plain asphalt
25% - LMD
25% CKD
25% CFA
25% HOFA

300

200

100

0
Neat Asphalt

30% Sulfur

5% SBS

Fig. 8 Bond strength versus SBS and sulfur-filler asphalt


blends

responsible for asphalt hardening. As the percentage


of sulfur increases, the amount of unreacted sulfur
increases in the asphalt medium, creating more sulfur
colloidal network within the mixture. This leads to the
continuous deterioration of the composite TBS.
Conventional roofing and waterproofing asphalt
polymer, styrene butadiene styrene (SBS), caused a
linear increment in the asphalts bond strength. 5 %
SBS resulted to more than three times the maximum
increment in bond strength the sulfur can yield at
20 %, as can be seen from Fig. 8.
The addition of sulfur to the SBS-modified asphalt
resulted in a material with higher bond strength and
elasticity than the SBS-only blend. The sulfur atom
tends to chemically react with the SBS polymer,
forming a cross-link between the polymer chain,
which leads to the evolution of a tough and sticky nonflowing asphalt composite. At 5 % SBS and 5 %
sulfur, the TBS value raised up to 50 % compared to
5 % SBS-only blend, due to the vulcanizing action of
the sulfur within the SBS polymer chain, as observed
from Fig. 8. The incremental trend continued for
higher content of SBS at 5 % sulfur. At SBS content
below 5 %, the vulcanizing effect is most likely to
form clusters of discrete patches of cross-linked
polymerized asphalt composite, due to insufficient
SBS polymer that will enable the formation of
continuous sulfur-reinforced polymer network. This
might even result in a material with lower strength
than the SBS-only blend.
The vulcanization temperature was a little above
150 C [15]. Once there is a sufficient amount of sulfur

and SBS additive (the average both on equal proportion by weight of asphalt) and the mixing temperature
is within the vulcanizing range with the material stored
within this temperature limit for the reaction to take
full form, the resulting composite will have superior
performance in terms of strength and elasticity than
the SBS-only mix.
The neat asphalts bond strength (TBS) was slightly
above 25 kN/m2. Adding filler to the asphalt generally
results to an increase in TBS, as observed from Fig. 8.
Both CKD and LMD have produced composites with
at least 100 % increase in bond strength compared to
the original asphalt at 25 % content, while the CFA
shows an insignificant increment (below 20 % that of
the neat asphalts). 25 % HOFA yields a material with
12 times BS of the pure asphalt.
Five percent SBS-modified asphalt exhibited
almost twice the bond strength possessed by the
25 % CKD and LMD containing asphalt. Adding
CKD, LMD or CFA to the 5 % SBS blend nearly
tripled its bond strength, but HOFA resulted to more
than just triple the bond strength, as can be seen from
Fig. 8. The 30 % sulfur mix has little additional TBS,
and even the addition of 25 % CKD, LMD or CFA
resulted in a material with lesser TBS than the neat
asphalt. HOFA has little effectiveness in raising the
TBS value in the sulfur blend, with an increase of not
more than 43 kN/m2.
3.7 Results of the analysis of variance
Both HOFA and sulfur significantly affected the SP of
sulfur-filler asphalt blends except the other two fillers,
LMD and CKD. All participating additives in the
sulfur-filler mixes caused a profound influence on the
ductility of the asphalt material. Apart from HOFA
filler, all other additives have a slight influence on the
penetration of the sulfur-filler mixes. Except for CKD
and LMD, all other additives (sulfur and HOFA)
significantly affected the viscosity of sulfur-filler
mastics. The summary of the result ANOVA is
presented in Table 4.
3.8 ASTM specifications
All blends containing sulfur failed to meet the
minimum flash point set-level for ASTM D 449
(Standard specification for asphalt used in damp
proofing and waterproofing), In addition to this, some

Materials and Structures (2015) 48:205216


Table 4 Summary of
statistical analysis result

215

Analysis of variance result obtained at 5 % significance level


Factors/additives

Tabular Fvalue

Calculated Fvalue

P value

Inference

Softening point (C)


Sulfur

3.4903

8.67

0.002

Significant

HOFA
Sulfur

3.2592
3.4903

25.64
4.44

0.000
0.026

Significant
Significant

CKD

3.2592

1.87

0.181

Insignificant

Sulfur

3.4903

13.33

0.000

Significant

LMD

3.2592

1.01

0.440

Insignificant

Ductility (cm)
Sulfur

3.4903

0.33

0.803

Insignificant

HOFA

3.2592

11.90

0.000

Significant

Sulfur

3.4903

6.20

0.009

Significant

CKD

3.2592

15.63

0.000

Significant

Sulfur

3.4903

4.26

0.029

Significant

LMD

3.2592

4.76

0.016

Significant

Penetration (dmm)
Sulfur

3.4903

3.47

0.051

Insignificant

HOFA

3.2592

7.76

0.003

Significant

Sulfur

3.4903

9.41

0.002

Significant

CKD
Sulfur

3.2592
3.4903

0.12
10.56

0.972
0.001

Insignificant
Significant

LMD

3.2592

0.62

0.659

Insignificant

Viscosity (cP)

The ANOVA result for


coal fly ash-only mastics is
not shown for table
consistency sake. But it
gives similar result as that
of CKD and LMD

Sulfur

3.4903

13.79

0.000

Significant

HOFA

3.2592

72.85

0.000

Significant

Sulfur

3.4903

43.61

0.000

Significant

CKD

3.2592

3.12

0.056

Insignificant

Sulfur

3.4903

55.57

0.000

Significant

LMD

3.2592

1.91

0.173

Insignificanta

sulfur mastics also dissatisfied the minimum ductility


benchmarks, otherwise they all might have been
classified under Type I material. HOFA-only mixes
are all Type II, and all the CKD- and LMD-only blends
fall under Type I category. Also, according to ASTM
D 312 (Standard specification for asphalt used in
roofing), majority of the sulfur-asphalt blends did not
pass the minimum flash point requirement. Some of
them did not also scale the minimum SP criteria. The
HOFA-only blends fall under Type I, and only 25 %
HOFA composite scrambled to be under Type II.
However, none of the LMD- and CKD-only blends
passed the minimum SP value, except for 20 and 25 %
LMD mixes which barely managed to scale and fall
under Type I. The CFA-only mastics fall under Type I

asphalt in both ASTM D 449 and ASTM D 312


specifications.

4 Conclusions and recommendation


High content of sulfur significantly reduced the bond
strength of filler-asphalt mix, but when used as a
vulcanizing agent along with polymer, it yielded a
superior tensile material than the SBS-alone composite. The vulcanizing effect of sulfur in polymer
modified asphalt will help minimize the amount of
the not so cheap polymer required for the manufacturing of certain asphalt waterproofing materials. All
the fillers affected the asphalt BS positively, with

216

HOFA having the greatest impact. Statistical analysis


of the asphalt physical test result shows HOFA to be
more effective than the other three fillers (LMD, CKD
and CFA) in increasing the SP and viscosity or in
reducing the asphalt ductility and penetration. The
significant drop in the flash point of sulfur-asphalt
affected its suitability for use in roofing applications.
Asphalt mastic bond strength test should be
standardized and included in the standard test methods
for preformed expansion joint filler for concrete
construction (ASTM D 545-08) and all other relevant
specifications.
Acknowledgments The authors acknowledge the supports
provided by King Fahd University of Petroleum and Minerals
and Saudi Arabian Oil Company (Saudi Aramco), Dhahran,
Saudi Arabia in carrying out this research.

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