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UTILIZATION OF BY-PRODUCED SULFUR FOR THE

MANUFACTURE OF UNMODIFIED SULFUR CONCRETE
Violeta Gracia
(1)
, Enric Vzquez
(2)
and Sergio Carmona
(3)

(1), (2) Materials Section, Department of Construction Engineering, Universitat Politcnica de
Catalunya, Spain
(3) Department of Civil Works, Universidad Tcnica Federico Santa Mara, Chile
Abstract ID Number: 257
Author contacts
Authors E-Mail Fax Postal address
Violeta Gracia violetagd@terra.es +34934017262
UPC Campus Nord, Edif. B-1,
Of. 108, C/ Jordi Girona, s/n.,
08034 Barcelona
Enric Vzquez enric.vazquez@upc.es +34934017262
UPC Campus Nord, Edif. B-1,
Of. 108, C/ Jordi Girona, s/n.,
08034 Barcelona
Sergio Carmona sergio.carmona@usm.cl +5632654115
UTFSM, Avda. Espaa 1680,
Casilla 110-V, Valparaso, Chile.
Contact person for the paper: Violeta Gracia
Presenter of the paper during the Conference: Violeta Gracia
11
Total number of pages of the paper (this one excluded): 10

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UTILIZATION OF BY-PRODUCED SULFUR FOR THE
MANUFACTURE OF UNMODIFIED SULFUR CONCRETE
Violeta Gracia
(1)
, Enric Vzquez
(2)
and Sergio Carmona
(3)
(1), (2) Materials Section, Department of Construction Engineering, Universitat Politcnica de
Catalunya, Spain
(3) Department of Civil Works, Universidad Tcnica Federico Santa Mara, Chile



Abstract
In the last decades the availability of sulfur has considerably grown in many countries.
This is mainly due to the current environmental restrictions regarding the petroleum and gas
refining processes, which limit the maximum quantity of sulfur present at combustibles.
Extremely large quantities of sulfur are thus obtained as a by-product of these processes,
together with coal processing and refining of copper in the mining sector.
The development of new applications for sulfur becomes fundamental. Sulfur concrete has
a relatively simple composition and manufacture, and very interesting characteristics and
properties. Its extremely high corrosion resistance, mechanical strength and fast hardening,
make it a high performance material suitable for several applications, especially the ones in
which other materials, fail.
A simple formulated sulfur concrete, made with unmodified sulfur, has been manufactured
and tested to demonstrate the feasibility of its utilization. Its microstructure has been studied
and its appropiate mechanical and environmental properties have been assured. Finally,
several applications for sulfur concrete have been proposed. It has been proved that the use of
unmodifed sulfur concrete can not be ruled out as it was in the past, as an interesting
construction alternative in areas where high level technology is not available.

Key words: sulfur, sulfur concrete, mechanical properties, microstructure, applications

1. INTRODUCTION
Sulfur concrete is not a new material; utilization of molten sulfur as a binder dates back to
the 17th century, when it was used to fix metal to stone, which was practical for quay-rings
used to anchor ships [1]. Such practises are believed to be in practise even today in Latin
America, and most likely elsewhere. In fact, there is evidence of even earlier uses of sulfur,
and both archaeological sites and classic literature offer proofs of sulfur knowledge and
utilisation as a binder. In 1859, Wright described the cementiteous properties of sulfur in a US
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Patent, but during the next 60 years there was almost no research about the use of sulfur in
construction.
During World War I, however, there was a very strong demand of sulfur, and several
deposits were opened in North America for their exploitation. This operation doubled the
annual production of sulfur in the United States and had as a consequence a surplus stock of
sulfur that enhanced the interest in developing new applications for this element.
In 1921, Bacon and Davis published a study about the use of surplus sulfur in the
manufacture of construction materials, and performed the first tests on this kind of materials.
They developed a mortar with 40% sulfur that was highly resistant to acids and had good
mechanical properties, and also started to study different additives to modify the properties of
sulfur in specific applications.
Duecker, in 1934, showed that the mortar proposed by Bacon and Davis suffered an
important volume fluctuation and cracking under thermal cycles, with loss in flexural
strength. This unstability comes from the fact that sulfur, after solidifying at 119C from
liquid state, undergoes a solid transformation at 95,4C between two crystalline structures:
monoclinic sulfur (S

), stable over that temperature, and orthorhombic sulfur (S

), stable
below 95,4C and at room temperatures. This transformation implies a densification, and thus
reduction of volume, which can produce an internal tensional state in sulfur. Sulfur is then
subject to cracking and disintegration under thermal cycles or other unstabilities.
In order to solve this trouble, Duecker modified the sulfur chemically with an olefin
polysulfur, known commercially as Thiokol, that delayed the volume change tendency and the
strength loss. Payne and Duecker (1940) developed the modification by additives, and the
possibility of having more stable cements lead to an increased industrial acceptance and
research of the product. The use of sulfur concrete for chemical plants was spread to certain
extent, especially for construction in acidid environments, in which the durability of the
material was excellent.
During the following 30 years, many efforts were devoted to the study of modifiers and
plasticizers for sulfur concrete, to avoid the mentiones problems. Most of the studied
substances were organic polymers of several types that, upon chemical reaction with sulfur,
induce the formation of polysulfurs and altere sulfur crystallization [2, 3, 4].
During the 1960s, there was a remarkable investment in environmental protection against
discharge of sulfur into the atmosphere, thus making sulfur a surplus commodity on the
market, particularly in the United States and Canada. This was a crucial point, that made the
interest to use sulfur as a structural binder to grow further, and initiated extensive research
programs which became very active in the 1970s and focusing on various properties of the
material, including durability.
Recent research programs on SC have been continuing to study different properties related
to the material performance, most of which are reported to be excellent. Based on literature
review and other reliable sources, it is evident that there will be a continuous abundant supply
of sulfur in the future due to strict global environmental regulations. The CEH Report8,
clearly indicates that global production of sulfur will continue to increase, thus assuring its
continued availability.
Construction materials such as Sulfur Concrete and Sulfur Asphalt continue to receive
more attention since they are environmentally friendly and cost-effective. Beginning in the
1970s, successful projects in which SC has been used as a construction material have been
carried out in different levels. However, most of these took place mainly in North America.
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During the same period, few and mainly research or test pilot projects have been carried out in
Europe, including Denmark, Sweden, Austria and United Kingdom, with only Denmark
conducting commercial or industrial activities on SC [5].
It is, therefore, not surprising that such environmental demands and the surplus sulfur draw
more attention for the use of SC as a construction material. Research activities on SC as a
construction material are currently reported to be going on in Spain, Italy, and The
Netherlands, while interest on medium scale industrial uses of SC plans are underway in
Poland. In South East Asia, preliminary reports are indicating a growing interest in the use of
SC as a result of the increase of surplus sulfur from refinery industry. Similar reports are from
the Middle East (Saudi Arabia), South America (Chile) and Africa (South Africa), where
attempts to use SC were reported earlier, or are in progress.
2. MANUFACTURE AND PROPERTIES
The main objective of this research was to develop a sulfur concrete with simple and clear
formulation, using unmodified sulfur, and having adequate physical, mechanical and
environmental properties for its utilisation; this would prove, in addition, the feasibility of
sulfur concrete manufacture using, as the binder, sulfur obtained as a by-product of petroleum
refining process. Other interests were to understand the physico-chemical behaviour of sulfur
concrete analysing its structure at microscale and to propose several applications for this
material, especially those where it could offer a great potential or amplify the current range of
uses.
The will to obtain a material that could be manufactured with locally available technology
lead to the decision of using only unmodified sulfur, a fact that would also establish a basis of
knowledge for future investigations on modified one. In order to control sulfur crystallisation
without chemical modification, a physical approach was taken: by the use of filler and well
graded aggregate, the intention was to create a dense network of nucleation points. In this
way, sulfur crystal growth would not be uncontrolled and a compact structure with small
crystals would be obtained, in which the adverse effects mentioned before would not be
significant enough to cause severe problems.
2.1 Feasibility and optimization
The first experimental approach to sulfur concrete included the optimization of both
formulation and manufacturing process. Sulfur obtained as a by-product at the Chilean
refinery RPC (Refinera de petrleo de ConCn), unmodified, was used as the binder, while
the aggregate was basaltic type, from the Aconcagua riverbed. A very strong attention was
paid to the granulometric curve of the aggregate, making adjustments in order to obtain a full
size distribution. In addition, substances added as mineral fillers were used to complete that
curve in the smaller size side; for that purpose, kaolin and carbon black were used because of
their previous cited uses for sulfur mortars and their local availability.
Sulfur mortars and concretes were manufactured using relatively simple equipment, and
different procedures were tested in order to minimize time and cost. Design of mixtures, or
dosification, was also optimised following criteria of both workability and mechanical
properties. Percentages of around 30% binder for sulfur mortars (maximum aggregate size 2,5
mm) and 15% binder for sulfur concretes (maximum aggregate size 10 mm) were found to be
the optimal for both manufacturing and performance, while the presence of mineral filler had
to be around 5% (mortars) to 10% (concretes) with respect to the mass of sulfur.
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2.2 Mechanical properties
Basic mechanical properties were measured for the samples in order to ensure that the
developed materials met the properties found in literature for these materials. Table 1 shows
some of the obtained results. As can be seen in the table, the obtained strengths turned out to
be very high. For sulfur mortars, compressive strengths were over 70 MPa, while flexural
strengths were over 12 MPa [6]. For sulfur concretes, compressive strengths were around 50
to 60 MPa and flexural strengths were 8-10 MPa [7]. It is worth mentioning, also, that these
strengths were reached after only a few hours; as an example, in the case of 101028 cm
samples, 80% of the maximum strength was obtained less about 3 hours after casting. This
fast hardening was studied also by measuring ultrasound speed and shrinkage evolution, and
the results, which confirmed the strength development results, are shown in figure 1. Tests at
large time scales (several months) were carried out in order to assure the conservation of these
mechanical properties in time.
Abrasion (wear) resistance tests, as well as other ones, gave also very positive results [8].
A special test for thermal cycling resistance was designed and implemented in order to
resemble a real situation that could be encountered by sulfur concrete in an outer application.
Samples of sulfur mortar were left for one year in a selected site in the Atacama desert (Chile)
were daily temperature has extreme variations, being able to reach 10C at winter nights, and
over 40C at midday sunlight in summer. The results were positive, too, showing only a slight
loss (around 5%) in indirect tensile strength after 365 thermal cycles of 30C amplitude.
Finally, fracture tests showed that the materials were more fragile than conventional
concrete; this fact has to be taken into account when proposing applications.

0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
0 60 120 180 240 300 360 420
Age (min)
S
h
r
i
n
k
a
g
e

(
m
m
/
m
)
3200
3300
3400
3500
3600
3700
3800
U
l
t
r
a
s
o
u
n
d

s
p
e
e
d

(
m
/
s
)
Shrinkage (mm/m)
Ultrasound speed
(m/s)

Figure 1. Comparison of the evolution of shrinkage and ultrasound speed during the first
hours after casting in samples of sulfur concrete (10mm max. size aggregate)

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Table 1: Mechanical properties of sulfur mortar and concrete [6, 7]
Property Results for sulfur mortar Results for sulfur concrete
Compressive strength (MPa) 70-75 50-60
Flexural strength (MPa) 12-13 8-10
Indirect tensile strength (MPa) 5-6 5
Shrinkage (mm/m) 0.6-0.7 1.4
2.3 Microstructure
Microstructure of sulfur mortars was studied by optical and electronic microscopy, and X-
ray diffraction spectrometry. As expected, in XRD analysis the only form of sulfur detected
was orthorombic sulfur, the stable one at room temperatures. There was an exception,
however, in two of the samples, in which a small quantity of monoclinic sulfur was detected,
although it was not present when tests were repeated several months after, indicating a late
but normal reversion to orthorhombic sulfur.


Figure 2: SEM images from a sulfur mortar with no added filler. Scale marks indicate 2mm
(upper left image), 70 m (upper right), 30 m (down left) and 6 m (down right).
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Scanning Electron Microscopy (SEM) has proved to be the most suitable tool to visually
study the structure of sulfur cements. Optical microscopy does not seem to be adequate for
that purpose, not only because of its poor resolution power and field depth, but also because
of the high homogeneity and low contrast that sulfur samples offer. SEM, on the contrary,
offers neat images with distinguishable features, and helps to understand the behaviour of this
kind of materials.
As general characteristics, it will be stated that samples were very homogeneous, with low
porosity and a high degree of packing in all cases. Sulfur was covering and binding very well
the aggregates and also filling the inner spaces in such a way that there was almost no
appreciable porosity, as it can be appreciated in the larger scale images in figures 2 and 3.
When the mix design was optimal, especially regarding aggregate grain size distribution and
filler, no large sulfur crystals could be observed, but a compact and homogeneous mix.
On the other hand, some common crystallization features were observed among the
samples. In the areas where sulfur shrinkage left voids, sulfur could develop some structures
that, although not having a considerable size (porosity was small and scarce), are examples of
typical sulfur crystals growth. Some of these patterns can be observed in the smaller scale
images in figures 2 and 3.


Figure 3: SEM images from a sulfur mortar with added filler. Scale marks indicate 2mm
(upper left image), 100 m (upper right), 100 m (down left) and 10 m (down right).
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All samples studied by SEM were made with well graded aggregate, that contained a
certain fraction of fines, but, in order to appreciate the influence of filler, different percentages
of it were used. Figure 2 shows images of a mortar with no added filler, while figure 3 shows
a mortar with a binder that contains 5% filler. The presence of filler has two main effects; at
large scales, the homogeneity is higher and the appreciable porosity is lower. At smaller
scales, the filler prevents the growth of crystals of considerable size; the patterns and features
observed in small scale images in figure 2 (no filler) are not found in the sample of figure 3,
in which only some superficial crystallisation was found at the walls of the scarce pores.
2.4 Environmental impact
The amounts of sulfates leached to the environment by sulfur mortars in leaching tests
were found to be well under the allowance limits, even those taken from the most strict
standards (Dutch regulations). In addition, recycling of sulfur concrete proved to be viable,
with an eventual improvement in its mechanical properties in some cases. Details can be
found in another paper presented in this congress by two of the authors.
3. CONSIDERATIONS ABOUT MODIFIED AND UNMODIFIED SULFUR
In order to have a proper criteria to evaluate the possibilities of unmodified sulfur concrete
and compare it to modified one, some samples of modified sulfur binder from different
companies that produce it were analysed through XRD. They were also melted in order to
study their behaviour in liquid state, specifically their fluidity properties.
Most of the obtained XRD diagrams showed only the presence of orthorhombic sulfur
(S

), with very high and narrow peaks, indicating that this was the only form of sulfur present.
In a few cases, in which sulfur was modifed with a very high percentage (20-25%) of
polymers, some monoclinic sulfur (S

) was detected, or the peaks of S

were not so
outstanding, suggesting the presence of a non-crystalline form of sulfur.
According to the observed behaviour, the chemical modification at small percentages may
not affect to the crystallization of sulfur directly (making sulfur crystallize in a structure
different than the stable one), but altere the behavior in the hot liquid mix period. The effect
of modification seems to be an increase in sulfurs degree of polimerization, or, in other
words, the existence of longer chains of sulfur. Sulfur itself possesses a high tendency to
polimerize; the chemical modifier would thus increase this tendency or maintain it for a
longer time.
As a consequence of that, sulfur's rheological properties are affected, presenting a higher
viscosity than unmodified one. This fact has an important effect in the crystallization of
sulfur. In a more viscous liquid, and in which the molecules are more polymerized, the growth
of the crystals will be more difficult and encounter more obstacles; it will be thus slower. This
fact can even be visualized in the cast samples.
Being the crystals growth slower, there is more time available for the development of
nucleation points, the starting points for the formation of crystals. The higher number of
nucleation points leads to the formation of a structure with smaller crystals, because these
crystals, when growing, encounter more obstacles and are not able to develop the typical large
needles of pure sulfur. In addition, as another consequence of the low velocity of crystal
growth, this structure shows a higher degree of arrangement. This fact, together with the
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smaller size of sulfur crystals, leads to a more packed and dense structure, with a probable
better performance under mechanical and thermal variations.
Of course it is also possible that, in addition to the above mentioned, the chemical
modification has also other effects, as the formation of new compounds at certain amounts by
the polimerization of sulfur and, especially, the combination of it with the polymeric
substances added as modifiers. This will even happen to a large extent for those formulations
with high percentages of modifier (around 20-25%), but, when polymer content is below 5%,
this will not be the main effect, as the XRD results have shown.
Taking these ideas into consideration, it is not surprising that unmodified sulfur concrete,
when correctly formulated and dosified, can have a performance similar to modified one in
certain cases. When the mix design is optimal, especially regarding aggregate grain size
distribution and filler, no large sulfur crystals are formed, but a compact and homogeneous
mix. Crystallization of sulfur, in this case, is controlled by the relative percentages and
distribution of space between aggregate, filler and binder, and the proper equilibrium between
them can play the role of the addition of chemicals in modified sulfur.
It must be kept in mind, however, that there is a difference between these two kinds of
sulfur concrete; unmodified sulfur seems to be more brittle than modified one, although more
precise fracture studies should be carried out. Therefore, the applications proposed in the next
section, while valid in principle for both types of sulfur concrete, should include some
limitations. Those elements where a small difference in toughness or degree of plasticity is a
critical factor should be manufactured with modified sulfur concrete, while unmodified one
would be an economical solution for applications of small size, not so critical conditions, or
recyclable ones.
4. APPLICATIONS
4.1 Precast elements
A first posible application is the fabrication of precast elements for their utilisation in
several areas. The characteristics of sulfur concrete that lead to consider this application are,
mainly, its high strength, the short time it gets to achieve it and the possibility of recycling.
High strength would assure the fullfilling of mechanical requirements, while its fast hardening
would allow an inmediate use with no necessity for long storage. And in case the element was
damaged, its reciclability would allow a simple and fast repair.
Some of the precast elements that could be manufactured are elements related to road
works (barriers, sidewalks, pedestals, etc), tiles and setts for interior and exterior pavements,
bricks for simple exterior structures, elements for sewer and drainage installations (sewer
pipes, manholes), elements in marine environment, for shoreline protection or dock
basements, railway and tramway sleepers, or electrolitic cells.
4.2 Wastes encapsulation
Conventional concrete has been used in several occasions as a matrix for the encapsulation
of contaminating or hazardous wastes. However, it presents some troubles in this application
that, in some cases, limit the percentage of wastes that can be included in the material, when
they are leached to teh environment through the porosity of concrete or may interfere in the
setting chemical reactions.
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Sulfur concrete has proved to be a highly impermeable material; the several tests carried
out by different researchers have shown that the leaching rates are extremely low, even the
leaching of sulfur that is, itself, a waste. In addition, its hardening by solidification is, in
general, less affected by the presence of several substances. These reasons make it a good
candidate for utilisation as a matrix or binder for the inmobilisation of wastes, mixing them
with the sulfur and the aggregates in the manufacturing process.
Some of the wastes that could be encapsulated in sulfur concrete are heavy metals, organic
wastes, residual aggregates from mining or other industries, ashes from wastes incineration,
and carbon industry, used tires, and wastes with content in sulfates, chlorides and other salts.
It is interesting to comment that a formulation of sulfur fully composed by wastes can be
developed. Sulfur is an important by-product of the gas and petroleum refining proceses, as
well as from carbon gasification, while wastes from mining industry may be used as
aggregates. And certain types of ash, like the one coming from carbon treatment facilities, can
be used as a filler.
Several companies are developing nowadays formulations of sulfur concrete that contain
hazardous wastes of special importance in several areas.
4.3 Pavements and coatings
The classical application of sulfur concrete has been, because of its extremely high
chemical and abrasion resistance, the construction of pavements and coatings in corrosive
industrial environments. This one can still be one of the main applications for this material,
although taking into account that the areas in which these sulfur concrete pavements can be
designed for can be diversified.
Some examples of the application of sulfur concrete in pavements and coatings are:
chemical plants floors, especially for acidic environments, floors for food processing plants,
roads and airport runways, paving in low temperature areas, coating of foundations, coating of
elements in marine environment.
It must be pointed out that the previous experiences in this kind of applications, especially
in the construction of corrosion resistance pavements, have been highly successful. The
prolonged durability shown by sulfur concrete, keeping its properties during long periods of
time, makes it one of the most promising applications field for this material.
4.4 Repairs
One of the most interesting properties of sulfur concrete is the little time it takes to harden
and attain a high percentage of its maximum strength. This characteristic propitiates a kind of
application in which it can offer great advantages: repairing. Some examples may be the
repairing of rigid (concrete) pavements [9], and urgent repairs in big industries.
Some repair experiences with sulfur concrete have taken place in the copper mining
industry in Chile, specifically in the channels that evacuate constantly the highly abrasive
liquid that comes from the mining process. Sulfur concrete has allowed not having to close
the channel as much time as if the repair work had been made with conventional concrete.
This implies, obviously, a great economical advantage, because it minimizes the influence of
repairs in the production, and it is especially important for big size industries, like the Chilean
example.
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5. CONCLUSIONS
Unmodified sulfur mortars and concretes have been developed, with excellent
mechanical properties and low environmental impact.
The viability of using sulfur obtained as a by-product of industrial processes has been
demonstrated by the used of sulfur from a petroleum refinery.
The use of unmodifed sulfur concrete can not be ruled out, as it has been happening in
the recent past. This material can represent a very interesting construction solution or
alternative in areas where, despite having a surplus of sulfur, high level technology is
not available.
Several applications have been proposed in which sulfur concrete offers a high potential
as a construction material, contributing at the same time to the sustainable development
of construction and industrial sectors.
ACKOWLEDGEMENTS
The authors wish to acknowledge the Department of Construction Engineering at the
Universitat Politcnica de Catalunya (Barcelona, Spain) and the Department of Civil Works at
the Universidad Tcnica Federico Santa Mara (Valparaso, Chile); both of them held the
main tasks for this research work. It is also acknowledged the collaboration from the Institute
of Earth Sciences "Jaume Almera" from the Spanish Research Council and the Department of
Materials Science and Metallurgy at the Universitat Politcnica de Catalunya (both in
Barcelona, Spain).
REFERENCES
[1] ACI, 'Guide for mixing and placing sulfur concrete in construction', Report 548.2R-88, (American
Concrete Institute, 1988).
[2] Blight L., Currell B.R., Nash B.J., Scott R.A.M. and Stillo C., 'Preparation and properties of
modified sulfur systems', New Uses of Sulfur - II, Advances in Chemistry Series 165 (American
Chemical Society, 1978), 13-30.
[3] Bordoloi B.K. and Pearce E.M., 'Plastic sulfur stabilization by copolymerization of sulfur with
dicyclopentadiene', New Uses of Sulfur - II, Advances in Chemistry Series 165 (American
Chemical Society, 1978), 31-53.
[4] Jordaan I.J., Gillott J.E., Loov R.E. and Shrive N.G., 'Improved ductility of sulphur concretes and
its relation to strength', Proceedings of the International Conference on Sulphur in Construction,
Ottawa, 1978 (CANMET, Energy, Mines and Resources Canada, 1978), 475-488.
[5] Makenya, A.R., 'Industrial Application of Sulfur Concrete. An Environment-friendly Construction
Material', Doctoral Thesis (KTH, Royal Institute of Technology, Stockholm, Sweden, 2001).
[6] Cordano I.P., 'Estudio experimental de morteros de azufre' (Universidad Tcnica Federico Santa
Mara, Valparaso, Chile, 2000).
[7] Coevas L.R., 'Estudio experimental de las propiedades mecnicas de hormigones de azufre'
(Universidad Tcnica Federico Santa Mara, Valparaso, Chile, 2000).
[8] Lillo J.A., 'Estudio de propiedades mecnicas en morteros y hormigones de azufre' (Universidad
Tcnica Federico Santa Mara, Valparaso, Chile, 2001).
[9] Carmona S. and Gracia V., 'Hormign de azufre: una alternativa viable para la reparacin de
pavimentos rgidos', Proceedings of the Conference PROVIAL99 (Rancagua, Chile, 1999).