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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
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
207
Magnitude
Ductility (cm)
150?
Penetration (dmm)
67.2
52
342
Viscosity (cP)
575
Weight (%)
Carbon
92.5
Magnesium
0.79
Silicon
0.09
Sulfur
5.80
Vanadium
0.61
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
15 %
25 %
20 %
208
209
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.
210
Softening Point, oC
65
60
55
50
45
40
0%
10%
15%
20%
25%
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
80
60
40
20
0
0%
10%
15%
20%
25%
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
212
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%
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
3000
2000
1000
0
0%
10%
15%
20%
25%
213
1000
100
10
0%
3%
5%
8%
10%
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%
30%
360
0%
20%
SBS/sulfur
25%
214
500
400
plain asphalt
25% - LMD
25% CKD
25% CFA
25% HOFA
300
200
100
0
Neat Asphalt
30% Sulfur
5% SBS
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
215
Tabular Fvalue
Calculated Fvalue
P value
Inference
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)
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
216
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