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DOI 10.1007/s00254-006-0631-4
O R I G I N A L A RT I C L E
Received: 7 September 2006 / Accepted: 18 October 2006 / Published online: 24 January 2007
Springer-Verlag 2007
Introduction
In the last decades, the availability of sulfur has considerably grown in many countries. This is mainly due
to the current environmental restrictions regarding
petroleum and gas refining processes, which limit the
maximum quantity of sulfur present in the combustibles. Extremely large quantities of sulfur are thus obtained as a by-product of these processes, for example,
in the United Arab Emirates (UAE), which is ranked
as the worlds fourth largest producer, natural gas reserves are of roughly 212.0 trillion cubic feet. The Abu
Dhabi National Oil Company (ADNOC) has placed
increasing emphasis on the development and uses of its
natural gas resources to meet the growing demand for
power generation, water desalination, petrochemical
plants and enhanced oil recovery. Concurrently, an
environmental priority has been given to recovering
and processing the associated gas.
The development of new applications for sulfur
becomes fundamental. Sulfur concrete has a relatively
simple composition and manufacture, and very interesting characteristics and properties. Sulfur concrete
123
160
123
161
Table 1 Comparison between the composition properties of
SPC and PCC (McBee and Weber 1990)
Strength (psi)
Compressive
Splitting tensile
Flexural
Coefficient of thermal
expansion (l in./in.)/C
Moisture absorption,
Air void content (%)
Elastic modulus 106psi
Specific gravity
Linear shrinkage (%)
Impact strength, ft-1b
Compressive
Flexural
Mix proportions (wt%)
Sulfur polymer cement
Water
Mineral filler
Portland cement
Sand
Coarse aggregate
a
b
Sulfur concretea
Portland
cement concreteb
7,00010,0000
1,0001,500
1,3502,000
3,5005,000
500
535
14.014.7
0.00.10
3.06.0
4.0
2.42.5
0.080.12
12
0.303.0
4.0
4.0
2.5
0.060.10
100119
0.30.5
81
0.2
1418
0
69
0
3842
3337
0
69
0
1218
30
45
123
162
Sand
Fly ash
CaO
Fe2O3
K2O
MgO
SiO2
0.47
32.4
16.35
0.46
0.676
4.34
0.13
0.027
1.158
0.66
74.4
60.9
Fly ash
Sieve mesh
size (mm)
Mass retained
Sieve mesh
on the sieve (%) size (mm)
Mass retained
on the sieve (%)
0.425
0.250
0.150
0.106
0.090
0.075
Bottom dish
0.00
8.82
49.90
24.64
8.80
4.85
3.00
0.40
1.25
2.85
13.35
12.25
46.80
18.35
4.75
0.250
0.150
0.125
0.075
0.063
0.053
0.045
Bottom dish
123
163
S0 S6 S0
S0 S6 S0
S8
S0 S6 S0 S8
etc.
However, above 140C, dehydrogenation of saturated bitumen components can occur; also linear
polysulfide can transform into stable cyclic thiophene
structures (Syroezhko et al. 2003). It is noted that
modified sulfur should be produced within its recommended mixing temperature range of 135141C.
Characterization of modified sulfur was performed
by different tools: a chemical analyzer was used to
determine the chemical composition of modified sulfur,
S: 97.4 0.48, C: 1.981 0.074 and H: 0.1 0.067,
which indicates that modified sulfur contains organic
compounds (related to the presence of C and H).
However, the reaction between bitumen and sulfur
should be determined by other means. To investigate
the nature of the chemical interaction between bitumen and sulfur, the completion of bitumen sulfur
reaction was strongly supported by IR measurement of
the characteristic double bonds in bitumen, which is
the main modifying bitumen constituent. Figure 1
shows the band at 2,975 cm1, which is consistent with
CH stretching. Since CH is associated with C=C
double bonds, the disappearance of CH bonds in the
modified sulfur spectra suggests the consumption of
aliphatic C=C bonds, which generally leads to the
polymerization of sulfur with bitumen. Negative peak
at 2,400 cm1 indicates the removal of NC=O group,
showing that they are sites of chemical reaction for
polysulfide formation. An increase in the relative
intensity in the spectra at 584 cm1, corresponds to
disulfide SS bond between adjacent thiol groups.
The obtained XRD diagrams for pure sulfur and
sulfur modified with a small amount of bitumen
(2.5 wt%) are shown in Fig. 2. XRD analysis confirms
that the modification of sulfur makes sulfur crystallize
with a structure different from the unmodified one.
Modified sulfur gives a sharp signal shifted to the lower
2-theta, which in turn indicates that the newly formed
structure is fine in its grain size.
Scanning electron microscope reveals how bitumen
controls the crystallization of sulfur. Pure sulfur crystallizes and forms dense, large alpha sulfur crystals (Sa)
with orthorhombic sulfur morphology as shown in Fig.
3a. With the addition of bitumen, the crystal growth is
limited and controlled by the bitumen in such a way
123
164
100
Transmittance (%)
b
95
90
100
98
96
85
a
b
94
92
90
3080
80
4000
3500
3000
2500
3010
2000
2940
1500
2870
2800
1000
500
Wavenumber (cm-1)
1500
Counter
1250
Pure Sulfur
Modified Sulfur
1000
750
500
250
0
20
22
24
26
28
30
2-Theta
(a)
(b)
123
165
Length
Width
Bitumen (wt%)
2.5
3.5
600
147
1000
167
1583
279
(a) 100
Weight (%)
80
60
40
20
0
200
100
300
400
500
600
Temperature (deg C)
(b)
50
119.25 deg C
Pure Sulfur
45
First run
Second run
40
Pure Sulfur
Modified Sulfur
112.58 deg C
35
30
25
103.5 deg C
20
90
100
110
120
130
120
130
45
Modified Sulfur
First run
40
118.58 deg C
Second run
35
117.92 deg C
30
25
20
90
98.92 deg C
100
110
Temperature (deg C)
123
166
Selected mix
y = -544.76x2 + 996.38x - 402.23
R-squared = 0.9561
50
40
30
20
0.6
0.7
0.8
0.9
1.0
1.1
y = -16.16x + 55.04
R-squared = 0.975985
50
40
35
30
0.0
0.2
0.4
0.6
0.8
1.0
123
167
b
atomic
%
O
22.9
Al
6.3
Si
23.5
S
38.3
K
2.5
Ca
1.6
Fe
4.9
Counts
Energy (KeV)
b
atomic
%
O
24
Al
7.1
Si
21.3
S
39.6
K
2.7
Ca
0.8
Fe
4.6
Counts
Cummulative (%)
Energy (KeV)
100.00
100
Sulfur Concrete
Porse
80
60
Sulfur Concrete
40
99.90
20
0
0.00
0.20
0.40
0.60
0.80
1.00
99.85
was found to be of good quality, showing a low concentration of impurities and grains with an irregular
geometry. This quality of sand grains may reduce the
workability of the mortar; in contrast, they enabled the
molten sulfur to adhere more easily to the surface of
the sand grains (Gemelli et al. 2004). Fly ash was found
to be an excellent agent for controlling the viscosity
and increasing the durability of the final product. The
rapid hardening and early strength gain changed over
time, resulting in a very high strength material with an
average compression of 54 MPa and modulus of elasticity of 1603 MPa. As a reference, it is worth noting
that for mortars made from Portland cement, the
strength properties were found to be 22 MPa for
Weight %
99.80
60
90
120
150
100
90
80
70
60
100
200
300
400
500
600
Temperature (deg C)
Fig. 10 TGA curves for SC and SPC, the heating rate was 20C/
min
123
168
30
Sulfur Concrete
Second run
Stress (Mpa)
First run
28
166.4
26
138.3
alpha crystal peak
24
30
20
Portland cement concrete
10
28.7
22
33.3
0
0.00
0.01
0.02
0.03
0.04
Strain (mm/mm)
20
90
100
110
120
130
28
153.1
First run
Second run
26
129.3
24
22
26.9
20
90
100
28.1
110
120
130
Temperature (deg C)
123
169
60
55
50
45
40
35
30
14
21
28
35
42
Age (day)
50
40
30
20
20
40
60
80
100
120
Temperature (deg C)
123
170
123
171
40
% Atomic sulfur
35
25
20
20
40
60
80
100
Temperature (deg)
Fig. 17 Change in the sulfur percentage in SPC, with temperature, data obtained from EDX results
sulfur polymerization with bitumen and increasing available sites for chemical reaction
that leads to polysulfide formation;
(b) forming a new structure with fine grain sizes;
(c) controlling crystallization of sulfur; pure sulfur
crystallizes and forms dense and large alpha
sulfur crystals with orthorhombic sulfur morphology; with the addition of bitumen, the
crystal growth is limited and controlled by the
bitumen in such a way that all crystals are
plate-like, of micron dimension and as monoclinic sulfur crystals of beta form;
(d) uniform distribution of bitumen within the
sulfur, leading to increased resistance to crack
formation and increased thermal stability;
(e) modification of sulfur mineralogy. Modified
sulfur remains in the monoclinic modification
of beta form and does not undergo a phase
transformation to the orthorhombic form
(alpha form) upon solidification. Addition of
bitumen does, however, prevent the growth
of macro sulfur crystals.
1.25
1.00
0.75
0.50
0.25
0.00
20
40
60
80
100
Temperature (deg)
Fig. 18 Percentage loss of weight of sulfur varied with temperature, data obtained from gravimetric analysis
2.
123
172
Cumulative (%)
SPC pores
80
40C
60C
60
80C
100C
40
20
0
0.0
0.2
0.4
0.6
0.8
1.0
(a)
S
Q
P
60C
Q
P
40C
80C
Q
S
P
100C
S
P
20
C
30
D H
A
40
50
60
70
2-Theta
(b)
(c)
123
(d)
(a)
Q
S
P
173
60C
S
P
40C
80C
S
P
100C
S
P
20
C
30
D H
A
40
50
60
70
2-Theta
(b)
SPC samples were prepared and maintained at constant temperatures of 26, 40, 60, 80, and 100C for
different periods of time. The manufactured SPC
developed 76% of its ultimate compressive strength
after 1 day, and 97% after 3 days. No significant
strength gain with time was observed. The compressive
strength of SPC was dependent on the temperature at
which the material was cured. For temperatures less
than 60C, SPC strength was higher than the PCC by
about 2030%. Whilst for temperatures higher than
60C and less than 100C, the compressive strength
remained within the range of PCC.
The microstructure analysis of the manufactured
SPC revealed that as temperature increased pore sizes
123
174
(a)
Q
S
P
Q
S
40C
60C
C
80C
Q
S
P
A
100C
S
P
20
C
30
D H
A
40
50
60
70
2-Theta
(b)
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