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Improving rubber concrete by waste organic sulfur compounds

Liang-Hisng Chou, Chun-Nan Lin, Chun-Ku Lu, Cheng-Haw Lee and Maw-Tien Lee
Waste Manag Res 2010 28: 29 originally published online 26 August 2009
DOI: 10.1177/0734242X09103843

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ISSN 0734–242X
Waste Management & Research
2010: 28: 29–35
DOI: 10.1177/0734242X09103843

Improving rubber concrete by waste organic sulfur

compounds
Liang-Hisng Chou, Chun-Nan Lin
Department of Civil and Water Resource Engineering, National Chiayi University, Chiayi City, Taiwan

Chun-Ku Lu, Cheng-Haw Lee

Department of Resource Engineering, National Cheng Kung University, Tainan City, Taiwan

Maw-Tien Lee
Department of Applied Chemistry, National Chiayi University, Chiayi City, Taiwan

In this study, the use of crumb tyres as additives to concrete was investigated. For some time, researchers have been studying
the physical properties of concrete to determine why the inclusion of rubber particles causes the concrete to degrade. Several
methods have been developed to improve the bonding between rubber particles and cement hydration products (C–S–H) with
the hope of creating a product with an improvement in mechanical strength. In this study, the crumb tyres were treated with
waste organic sulfur compounds from a petroleum refining factory in order to modify their surface properties. Organic sulfur
compounds with amphiphilic properties can enhance the hydrophilic properties of the rubber and increase the intermolecular
interaction forces between rubber and C–S–H. In the present study, a colloid probe of C–S–H was prepared to measure these
intermolecular interaction forces by utilizing an atomic force microscope. Experimental results showed that rubber particles
treated with waste organic sulfur compounds became more hydrophilic. In addition, the intermolecular interaction forces
increased with the adsorption of waste organic sulfur compounds on the surface of the rubber particles. The compressive, tensile
and flexural strengths of concrete samples that included rubber particles treated with organic sulfur compound also increased
significantly.

Keywords: cement-rubber composite, recycling, organic sulfur compounds

Introduction
A large amount of waste tyres are generated all over the
world every year. For example, more than 270 million scrap
tyres are produced in the United States each year (Siddique
& Naik 2004). In Taiwan over 10 million scrap tyres are pro-
duced every year and nearly 70% of them undergo shredding
and grinding processes (Chang 2008). As waste tyres are not
easily biodegradable after a long period of landfill, this is not
only an environmental problem but also a waste of natural
resources. It has been suggested that rubberized concrete
could be used, for example, in highway construction as a shock
absorber, in sound barriers as a sound absorber, in buildings
as an earthquake shock-wave absorber, or in impact preven-
tion structures such as Jersey barriers. It is believed that such
concrete can also be used in soil and water conservation con-
struction materials. As the rubberized concrete is a useful
material, many studies on the use of rubber particles as addi-
tives in concrete have been reported in the literature, (Eldin
& Senouci 1992, 1993a, b, Lee et al. 1993, 1998, Topcu 1995,
1997, Fattuhi & Clark 1996, Toutanji 1996, Huynh & Ragha-
van 1997, Topcu & Avcular 1997, Li et al. 1998, Raghavan et
al. 1998, Khatib and Bayomy 1999, Ali et al. 2000, Segre &
Joekes 2000, Nehdi & Khan 2001, Hernandez-Olivares et al.
2002, Chou et al. 2003, 2004, Pierce & Blackwell 2003, Hern-
andez-Olivares & Barluenga 2004, Segre et al. 2004, Siddique
& Naik 2004). Most of the studies are practical and experi-
mental in nature without a theoretical basis. Chou et al.

Corresponding author: M.T. Lee, Department of Applied Chemistry, National Chiayi University, Taiwan.
E-mail: mtlee@mail.ncyu.edu.tw
Received 6 October 2008; accepted in revised form 4 January 2009
Figures 1, 2, 4–8 appear in color online: http://wmr.sagepub.com

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L.H. Chou, C.K. Lu, C.H. Lee, C.N. Lin, M.T. Lee
(2007) proposed a theoretical analysis to explain the effect of
rubber additives on the physical properties of the concrete. In
their study they coupled experimental observations with the-
oretical derivation, and showed that the added rubber particles
could disturb water flow in the rubberized concrete as a result
of the variation of intermolecular interaction forces, leading to
insufficient and imperfect hydration in some regions. These
regions of insufficient hydration weaken the concrete, result-
ing in reduced compressive strength. Summarizing the litera-
ture, it is widely believed that the reduction of the compres-
sive strength of concrete with rubber addition is mainly
attributable to the reduced adhesion between the interface
between cement and rubber grains. To improve the compres-
sive strength, most authors tried to modify the surface proper-
ties of the rubber particles to enhance its adhesion to C–S–H.
In this study, waste organic sulfur compounds from petro-
leum refining factory were used to modify the surface of
crumb tyre particles to enhance its hydrophilic properties.
They also enhanced the intermolecular interaction forces
between crumb tyre particles and C–S–H and increased the
strengths of rubber concrete.
Materials and methods
A solution of organic sulfur compounds from a petroleum
refining factory was used to modify the surface properties of
the rubber particles. The nature of the waste tyres used was
SBR + natural rubber, produced by Cheng-hsing Rubber Co,
Taiwan. Sand which had composition: SiO2, 96.83%; Fe2O3,
0.086%; and Al2O3, 1.674% and was supplied by Taiwan Chin
Ching Company, was used in the experiments. The waste
rubber tyres were mechanically ground at a temperature that
was below the ductile-to-brittle temperature, screened to 30
to 50 meshes and used as the additive. To prepare the rubber
specimens for surface tension measurement, rubber was dis-
solved in CS2, coated on a smooth glass surface and air-dried
at room temperature in a close chamber. As the CS2 evapo-
rated completely, the rubber was cleaned with acetone and
distilled water to remove possible contaminants on the sur-
face. The surface roughness of the rubber specimen was
observed with an atomic force microscope (AFM). In order to
understand the effects of organic sulfur compounds on contact
angles, the clean rubber specimen was immersed in the solu-
tion of organic sulfur compounds and dried at room tempera-
ture. An optical microscope was used to observe the adsorp-
tion of organic sulfur compounds on the rubber surface.
Advancing and receding contact angles of the rubber were
measured with a Kruss k121 tension meter based on the Wil-
helmy method. To measure the intermolecular interaction
forces, a colloid probe with C–S–H was prepared according
to the method proposed by Plassard et al. (2005).
The first type of Portland cement produced by Taiwan
Cement Co. was used to prepare specimens for strength test.
Two types of rubberized specimens were prepared. The first
group of specimens was prepared without adding sand. They
were used for observing the dynamics of changes of the sur-
face structure. The second group of specimens was prepared
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by adding sand and rubber particles. They were prepared in
cubic moulds to facilitate the physical testing. Rubber addi-
tion levels of 0, 3 and 6% by weight were tested. All speci-
mens were prepared with a water/cement ratio of 0.5 to
ensure there was sufficient water in the paste. The measure-
ments of compressive, flexural, and tensile strength of the
specimens were conducted according to American Society of
Testing and Material (ASTM) C109, C190 and C348. For sta-
tistical evaluation, nine samples were made for each experi-
ment.
Results and discussion
Effect of organic sulfur compounds on wetability of rubber
surfaces and intermolecular interaction forces
The surface roughness of the rubber for contact angle meas-
urement was as shown in Figure 1. The surface roughness
was about 0.1 µm. Figure 2 is an optical microscope picture of
rubber treated with organic sulfur compounds. It is obvious
that the organic sulfur compounds adsorbed onto the surface
of rubber. With the amphiphilic properties of the organic sul-
fur compounds, the modified rubber had more hydrophilic
properties. Advancing and receding contact angles are shown
in Table 1. For the untreated rubber, the advancing and reced-
ing contact angles in water were 103 and 59°, respectively. On
the other hand, rubber treated with organic sulfur compounds
gave advancing and receding contact angles of 100 and 31°,
respectively. The big difference in advancing contact angle
and receding contact may have been induced by the surface
roughness of the rubber. It is apparent that treating with
organic sulfur compounds can reduce the contact angle and,
thus, enhance the hydrophilic properties of the rubber sur-
faces.
Figure 3 shows a colloid probe of C–S–H. In this picture,
C–S–H grew at the end of the probe as depicted in the block.
The intermolecular interaction forces between the C–S–H
colloid probe and the rubber is shown in Table 2. For
untreated rubber the mode of the intermolecular interaction
forces was 25 nN and for rubber modified with organic sulfur
Table 1: Contact angles.
Contact angles
Materials
Advancing Receding
Untreated crumb rubber 103.23 59.46
Treated crumb rubber with 99.88 31.11
organic sulfur
Table 2: Intermolecular interaction forces.
Interaction forces Mode
Materials
(nN) (nN)
Untreated crumb rubber 15~30 25
Treated crumb rubber with 50~70 55
organic sulfur

Fig. 1: Surface roughness of rubber.
Fig. 2: Image of rubber surface, 400×: adsorption of organic sulfur
compounds on rubber surface.
compounds it was 55 nN. It is obvious that the rubber sam-
ples treated with organic sulfur compounds had greater
interaction forces with C–S–H than the untreated rubber
samples.
Dynamics of surface structure changes
By treating the rubber particles with organic sulfur com-
pounds, the cracking of the rubberized paste was successfully
prevented. A comparison of the surface structure changes of
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Improving rubber concrete by waste organic sulfur compounds
Fig. 3: Colloid probe with C–S–H.
the untreated rubber cement paste and rubber cement paste
modified with organic sulfur compounds at 50 min and 24 h
are shown in Figures 4 and 5, respectively. Figure 4 shows
that rubber particles treated with organic sulfur will delay the
hydration of cement. However, with the increase of time as
shown in Figure 5, the hydration of cement in the neighbor-
hood of rubber particles treated with organic sulfur com-
pounds was more uniform than that of untreated rubber
particles. The box shown in Figure 5(a) provides evidence
that the specimen containing untreated rubber crack near
31
L.H. Chou, C.K. Lu, C.H. Lee, C.N. Lin, M.T. Lee

Fig. 4: Surface structures of cement paste (50 min): (a) untreated crumb rubber; (b) crumb rubber with organic sulfur.

Fig. 5: Surface structures of cement paste (24 h): (a) untreated crumb rubber; (b) crumb rubber with organic sulfur.

the regions of rubber particles after 24 h. The surface struc-
ture changes of the rubberized cement paste containing
rubber that had been modified with organic sulfur com-
pounds shows no apparent cracking after 24 h as shown in
Figure 5(b). The area where cracking is visible in Figure 5(a)
appears to be incompletely hydrated due to insufficient
available water. It is particularly noteworthy that the crack-
ing is not at the interface of cement and rubber as expected
from the literature. It is, however, similar to that shown in a
previous study (Chou et al. 2007). It is obvious that the crack-
ing of the specimen will affect the mechanical properties
greatly.
Effect of the addition of waste tyre crumbs on the
mechanical strength of the specimens
For statistical evaluation, nine samples were made for each
experiment and the results are shown in Figures 6 to 8. The
average values for 28 days are also summarized in Table 3. In
the table, CCR, UCR, and SCR denote control samples
without crumb rubber, samples containing untreated crumb
rubber, and samples containing crumb rubber that had been
treated with organic sulfur, respectively. The subscripts 3 and
6 denote samples that include 3 and 6% rubber, respectively.
In comparison with the control specimen, the addition of
untreated waste tyre weakens the compressive, flexural and

Table 3: Mechanical strength of specimen (deviation).

Specimens Compressive strength Flexural strength Tensile strength

(kgf cm–2) (kgf cm–2) (kgf cm–2)

CCR 318.17 (2.57) 65.48 (0.10) 83.00 (1.82)
UCR 3% 268.09 (7.71) 52.00 (0.27) 67.11 (2.49)
UCR 6% 187.17 (7.72) 49.98 (0.21) 58.67 (2.45)
SCR 3% 287.14 (8.64) 59.54 (0.27) 75.68 (2.62)
SCR 6% 224.45 (9.47) 57.84 (0.33) 66.59 (2.84)
CCR, controlled samples without crumb rubber; UCR, with untreated crumb rubber; UCR 3%, 3% rubber; UCR6%, 6% rubber; SCR, with
organic sulfur modified crumb rubber; SCR 3, 3% rubber; SCR 6, 6% rubber.

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 Improving rubber concrete by waste organic sulfur compounds

Fig. 6: Compressive strength.

Fig. 7: Flexural strength.

Fig. 8: Tensile strength.

tensile strengths of the specimens significantly. For speci- strength and tensile strength at 28 days were decreased from
mens with 3% rubber, the compressive strength, flexural 318.17 to 268.09 kgf cm–2, 65.48 to 52.0 kgf cm–2 and 83.0 to

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L.H. Chou, C.K. Lu, C.H. Lee, C.N. Lin, M.T. Lee
67.11 kgf cm–2, respectively (Table 3). For specimens with 6%
rubber, the compressive strength, flexural strength and tensile
strength were decreased to 187.17, 49.98 and 58.67 kgf cm–2,
respectively. In terms of percentage, for specimens with 3%
rubber the reductions were 15, 20 and 19% for compressive,
flexural and tensile strength, respectively. For specimens
with 6% rubber, the reductions in compressive, flexural and
tensile strength were 41, 23.6 and 29%. The addition of crumb
rubber impacted significantly on the mechanical strength. It
is tempting to conclude that rubberized concrete that contains
untreated crumb rubber should only replace regular concrete
for applications in which the strengths are not critical.
Effect of organic sulfur compounds pretreatment of rubber
on mechanical strength of the specimens
Pretreatment of the rubber particles with organic sulfur com-
pounds improved the compressive strength of the rubberized
specimen significantly. The compressive strength, the flexural
strength and the tensile strength of the control sample with-
out rubber and two rubberized samples at 28 days are
shown in Table 3. As expected, the specimens containing
rubber particles that had been modified with organic sulfur
compounds showed better performance than specimens
containing untreated rubber. For specimens with 3% rub-
ber the increases in the compressive, flexural and tensile
strength due to treatment of the waste rubber crumb with
organic sulfur compounds were 268.09 to 287.14 kgf cm–2,
52.0 to 59.54 kgf cm–2 and 67.11 to 75.68 kgf cm–2, respec-
tively. For samples containing 6% treated rubber the cor-
responding increases in compressive, flexural and tensile
strength were 187.17 to 224.45 kgf cm–2, 49.98 to 57.84 kgf cm–2
and 58.67 to 66.59 kgf cm–2 In percentage terms, for speci-
mens with 3% rubber the increases in the compressive, flexu-
ral and the tensile strength due to organic sulfur compounds
treatment of the crumb rubber were 7.1, 14 and 12.7%, respec-
tively, and for samples containing 6% crumb rubber, the corre-
sponding increases were 19.9, 15.7 and 13.5%, respectively.
Thus, the treatment of waste rubber tyre crumbs with organic
sulfur compounds increased the mechanical strength rather
significantly for specimens containing 6% treated rubber
compared with that of specimens containing 3% treated rub-
ber. Two important factors affected the mechanical strength
of concrete that contained rubber crumbs treated with organic
compounds. With the adsorption of organic sulfur compounds
onto the surfaces of the rubber crumbs, the decrease in the
contact angles of rubber in water enhanced the film flow of
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The addition of rubber particles leads to the degradation of
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