Effect of polymer cement modifiers on mechanical and physical properties of polymer-modified mortar using recycled artificial marble waste fine aggregate

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Journal of Industrial and Engineering Chemistry 14 (2008) 265–271
www.elsevier.com/locate/jiec

Effect of polymer cement modifiers on mechanical and
physical properties of polymer-modified mortar using
recycled artificial marble waste fine aggregate
Eui-Hwan Hwang *, Young Soo Ko, Jong-Ki Jeon
Department of Chemical Engineering, Kongju National University, 275 Budae-dong, Cheonan, Chungnam-do 330-717, Republic of Korea
Received 29 October 2007; accepted 11 November 2007

Abstract
Various polymer-modified mortars using recycled artificial marble waste fine aggregate (AMWFA) were prepared and investigated for the
purpose of feasibility of recycling. Styrene–butadiene rubber (SBR) latex and polyacrylic ester (PAE) emulsion were employed as polymer
modifier, and compared each other. The replacement ratio of AMWFA was also changed to investigate the effect of it on physical properties.
Adding polymer cement modifier into mortar reduced water–cement ratio, and PAE was the more effective polymer cement modifier to reduce
water–cement ratio than SBR. PAE emulsion-modified mortar increased the air content entrained as the proportion of PAE was increased. There
was little difference in water absorption between SBR latex and PAE emulsion. The compressive strength decreased in the presence of polymer
cement modifiers compared to that of no polymer cement modifiers, but the compressive strength of 20% of polymer–cement ratio was higher than
that of 10%. After the hot water resistance test, both compressive strength and flexural strength were decreased.
# 2007 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Keywords: Polymer cement modifier; Polymer-modified mortar; Recycling; Recycled waste material

1. Introduction
It has been significantly important to develop the technology
to treat or recycle the waste from organic materials such as
plastics, vehicle tires, and artificial marble due to the enormous
production of them as the industry and economy of the world
are growing [1–3].
There have been several ways to treat the wastes such as

landfill, incineration, chemical recycling, material recycling
and the utilization of energy from combustion [4–12]. Most
methods excluding material recycling are known to have
critical limitations in economic, technical and environmental
manners [10,13–15]. Material recycling is expected to be more
feasible in a way that the simplicity of pretreatment, and the
reduction of energy consumption and environment pollution
can be satisfied [1,10,14,16].
A recent trend and preference of the interior decoration or
housing construction material is known to be of higher quality

* Corresponding author.
E-mail address: (E.-H. Hwang).

and more ornamental than the past, making use of a huge
amount of acrylic artificial marble as construction material.
Consequently, this links to the huge amount of waste artificial
marble, causing the environmental issue in our society.
Furthermore, the waste artificial marble is categorized and
treated as industrial wastes. It means it should be disposed or
burned to destroy, resulting in the air pollution and environmental pollution [13,14]. The importance of how to recycle or
reuse waste artificial marble became an important technological
issue recently, and a countermeasure was usage of the waste
artificial marble as an aggregate in the production of mortar
[17]. However, the recycling of waste artificial marble could
cause lowering of the performance or mechanical properties of
the final mortar [17].
An organic polymer or resin, so-called polymer modifier is
expected to overcome the problems described above because
the polymer-modifier is well known to offer to the final mortar

the improvement of higher strength, durability, good resistance
to corrosion, and strong resistance to damage from freeze-thaw
cycles [18–28].
In this study the polymer-modified mortars using recycled
artificial marble waste fine aggregate (AMWFA) were

1226-086X/$ – see front matter # 2007 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2007.11.002


266

E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

Table 1
Physical properties of polymer cement modifiers
Type

Specific
gravity
(20 8C)

Viscosity
(20 8C, cP)

pH
(20 8C)

Total
solids

(wt%)

SBR
PAE

1.020
1.054

171
28

9.2
8.8

49.1
54.2

investigated in detail with two different polymer-modifiers to
overcome the drawbacks like losing mechanical properties of
the mortar using AMWFA. Styrene–butadiene rubber (SBR)
latex and polyacrylic ester (PAE) emulsion were employed as
polymer modifier, and compared each other. The effect of
replacement ratio of AMWFA on the physical properties and
mechanical properties were also investigated and reported in
this article.

specimen so that the flow values of final mortar were fixed at
170 Æ 5 mm following KS F 2476. The specimens were
prepared using the mold in the dimension of 40 mm Â
40 mm  160 mm. Those were cured in a humid condition

at 20 Æ 2 8C and 90% of relative humidity for 2 days, cured
again in water at 20 8C for 5 days, and then cured in air at
20 Æ 2 8C and 60 Æ 10% of relative humidity for 21 days in a
thermo-hygrostat consecutively [29,30].
2.3. Test of air content, unit weight and flow value
The air content and unit weight of fresh polymer-modified
mortars were tested in accordance with JIS A 1174 and flow
value of fresh polymer-modified mortars was tested in
accordance with KS L 2476.
2.4. Test of hot water resistance and pore diameter
distribution

2. Experimental
2.1. Materials
Conventional Portland cement (OPC, type 1) and standard
sand were used throughout this study. Waste artificial marble
fine aggregate was acquired from the production process of
acrylic artificial marble, and it was crushed to get the fine
aggregate. SBR and PAE were purchased and utilized in the
form of latex and emulsion, respectively without any further
treatment. Table 1 shows the physical properties of two polymer
cement modifiers.
2.2. Preparation of specimens
The contents of polymer modifiers in polymer–cement
mixture were 0, 10 and 20 wt% as shown in Tables 2 and 3. The
replacement ratios of AMWFA for the sand were 0, 25, 50, 75
and 100%. Water–cement ratio was adjusted specimen by

Specimens were cured in water at 90 8C for 28 days, and
then were measured for compressive and flexural strengths. The

pore distribution was measured with mercury porosimeter for
the particle from specimen which had particle diameter of 2.5–
5 mm after washed with acetone and dried for 48 h.
3. Results and discussion
3.1. Variation of water–cement ratio
As shown in Fig. 1, water–cement ratio was increased as the
replacement ratio of AMWFA in mortar increased without
polymer modifier. However, adding polymer modifier into
mortar reduced water–cement ratio significantly. In case of
SBR latex and PAE emulsion, the content of 20 wt% results in
decrease in water–cement ratio by 28% and 55%, respectively,
meaning PAE was the more effective polymer modifier to
reduce water–cement ratio in this mortar system than SBR.

Table 2
Mix proportion of SBR polymer-modified mortars containing artificial marble waste fine aggregate
Cement:(sand + AMWFA)
(by weight)

AMWFA/
(AMWFA + sand) (wt%)

1:3.00
1:2.75
1:2.50
1:2.25
1:2.00

0
25

50
75
100

1:3.00
1:2.75
1:2.50
1:2.25
1:2.00
1:3.00
1:2.75
1:2.50
1:2.25
1:2.00

W/C
ratio (%)

Unit
weight (g/ml)

Air
content (%)

Flow
value

0

70.1

73.6
77.3
79.8
82.6

1.961
1.709
1.541
1.434
1.364

8.5
14.9
16.4
18.0
19.5

170
168
165
173
169

0
25
50
75
100

10

61.6
67.3
71.0
75.1
77.3

1.605
1.479
1.395
1.291
1.151

24.6
25.0
25.0
25.6
26.2

168
169
168
170
175

0
25
50
75
100

20

42.3
48.5
49.5
50.0
51.0

1.577
1.384
1.199
1.115
1.053

26.1
29.6
31.5
32.7
34.2

174
165
175
175
170

AMWFA: artificial marble waste fine aggregate.

P/C ratio

(wt%)


E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

267

Table 3
Mix proportion of PAE polymer-modified mortars containing artificial marble waste fine aggregate
Cement:(sand + AMWFA)
(by weight)

AMWFA/
(AMWFA + sand) (wt%)

1:3.00
1:2.75
1:2.50
1:2.25
1:2.00

0
25
50
75
100

1:3.00
1:2.75
1:2.50

1:2.25
1:2.00
1:3.00
1:2.75
1:2.50
1:2.25
1:2.00

P/C ratio
(wt%)

W/C
ratio (%)

Unit weight
(g/ml)

Air content
(%)

Flow
value

0

70.1
73.6
77.3
79.8
82.6

1.961
1.709
1.541
1.434
1.364

8.5
14.9
16.4
18.0
19.5

170
168
165
173
169

0
25
50
75
100

10

44.4
36.2
37.8

40.3
41.7

1.531
1.328
1.195
1.120
1.034

31.6
37.3
40.4
41.5
42.0

170
175
166
175
173

0
25
50
75
100

20

34.2

21.2
22.3
23.6
24.9

1.510
1.325
1.218
1.106
1.020

33.2
38.7
41.2
42.2
43.1

171
165
168
172
174

The water absorption of cement paste in AMWFA could be a
reason for the increase in water–cement ratio with higher
replacement ratio. Polymer modifier is known to improve
flowability, water resistance, and ball-bearing effect due to the
better dispersion of antifoaming agent and air-entrainment
during forming admixture [29], resulting in the decrease in
water–cement ratio for the mortar with polymer-modifier. PAE

emulsion is more air-entrainment than SBR latex, suggesting
that PAE emulsion is more effective to reduce water–cement
ratio in mortar.
3.2. Air content and unit weight

case that the AMWFA replace ratio was 50%, the air content of
SBR-modified mortar were 16.4, 25.0 and 31.5 for the SBR
proportion of 0, 10 and 20%, respectively, whereas those PAEmodified mortar were 16.4, 40.4, and 41.2% for the PAE
proportion of 0, 10 and 20%.
The change in the unit weight of the fresh mortars was
dependent on the replacement ratio of AMWFA as shown in
Fig. 3. Regardless of the absence and presence of polymer
cement modifier, the unit weight decreased significantly with
increasing the replacement ratio of AMWFA. It should be
considered that the specific gravity of AMWFA is lower than
that of standard sand and that the presence of polymer cement
modifier increased the air content entrained.

Fig. 2 exhibits the change in air contents in the fresh
polymer-modified mortar in a function of the replacement ratio
of AMWFA. SBR latex-modified mortar increase air content
entrained as the proportion of SBR latex was increased from 0
to 20 wt%, whereas PAE emulsion showed no significant
difference in air content entrained between 10 and 20 wt%. In

Water absorption was measured after the curing steps
described in Section 2. There was little difference in water
absorption between SBR latex and PAE emulsion as shown in

Fig. 1. Variation of water–cement ratios vs. replacement ratios of artificial

marble waste fine aggregate.

Fig. 2. Variation of air contents vs. contents of artificial marble waste fine
aggregate.

3.3. Water absorption


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E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

Fig. 3. Variation of unit weight ratios vs. contents of artificial marble waste fine
aggregate.

Fig. 5. Compressive strengths of polymer-modified mortars vs. contents of
artificial marble waste fine aggregate.

increased significantly in the presence of polymer cement
modifiers, whereas it decreased as the replacement ratio
increased. The improvement of flexural strength is linked to the
nature of polymer that is known to be flexible than cement
hydrate and other inorganic materials [29]. The flexural
strength of SBR-modified mortar with 20% of polymer–cement
ratio was about 47% higher than that of no polymer
modification at the replacement ratio of AMWFA of 50%.
3.5. Mechanical strength after hot water resistance test

Fig. 4. Variation of water absorption vs. contents of artificial marble waste fine
aggregate (before hot water immersion).

Fig. 4, and it was decreased drastically at 20% of polymer–
cement ratio for both SBR and PAE, resulting from a very good
water-resistant bond between the polymer cement modifier and
the cement components. AMWFA having the property of high
water absorption resulted in higher water absorption with
higher replacement ratios.

As shown in Fig. 7, the compressive strength after
immersing the specimen in hot water of 90 8C was lower than
it was before the immersion. The compressive strength was
lowered significantly after the hot water resistance test,
suggesting that the deterioration or decomposition of polymer
cement modifier at high temperature causes the change in
strength. There was little difference between SBR latex and
PAE emulsion in hot water resistance, but as the replacement
ratio of AMFWA increased, the compressive strength
decreased. The increase rate of compressive strength of 20%

3.4. Mechanical strength
Compressive strengths and flexural strengths were measured
and summarized in Figs. 5 and 6, respectively. The compressive
strength decreased in the presence of polymer cement modifier
compared to that of no polymer cement modifiers, but the
compressive strength of 20% of polymer–cement ratio was
higher than that of 10%. The polymer-modified mortar has
cement hydrate–cement hydrate bond and cement hydrate–
polymer bond [29]. Cement hydrate–polymer bonds are weaker
in compressive strength than cement hydrate–cement hydrate
bonds. However, the higher proportion of polymer modifier, the

higher sealing effect is shown, resulting in the improvement of
compressive strength. The flexural strengths of mortar

Fig. 6. Flexural strengths of polymer-modified mortars vs. contents of artificial
marble waste fine aggregate.


E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

Fig. 7. Compressive strengths of polymer-modified mortars vs. contents of
artificial marble waste fine aggregate (—: before hot water immersion, . . .: after
hot water immersion).

Fig. 8. Flexural strengths of polymer-modified mortars vs. contents of artificial
marble waste fine aggregate (—: before hot water immersion, . . .: after hot
water immersion).

269

Fig. 9. Comparison of total pore volume vs. contents of artificial marble waste
fine aggregate before/after hot water immersion test (PAE polymer–cement
ratio: 20 wt%).

Fig. 10. Comparison of bulk density vs. contents of artificial marble waste fine
aggregate before/after hot water immersion test (PAE polymer–cement ratio:
20 wt%).

of polymer–cement ratio had a lower value than that of 10% for
both SBR and PAE, resulting from the higher proportion of
polymer which was deteriorated or decomposed at high

temperature.
The flexural strength was measured after immersing the
specimen in hot water of 90 8C, and shown in Fig. 8. The rate of
decrease in flexural strength was similar between PAE-modified
mortar and SBR-modification. As the replacement ratio of WCFA
increased, the flexural strength as well as compressive strength
decreased. The flexural strength is closely affected by the bonding
strength of polymer itself and an overall improvement in cement
hydrate–aggregate bond [29,30–33], and the hot water resistance
test leads to the weakening of this bonding due to the deterioration
or decomposition of polymer [29,34].
3.6. Pore volume and density
The pore volumes of the specimen before and after hot
water resistance test were measured as depicted in Fig. 9.

Fig. 11. Comparison of average pore diameter vs. contents of artificial marble
waste fine aggregate before/after hot water immersion test (PAE polymer–
cement ratio: 20 wt%).


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E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

The total pore volume increased as the replacement ratio of
AMWFA increased significantly, resulting from that the
higher the amount of AMWFA, the higher the amount of air
entrained during the mixing process.
The reason for the significant decrease of total pore volume
after the hot water resistance test could be the progress of

hydration reaction of cement paste. The decrease of total pore
volume is also closely linked to the slight increase in the density
of the specimen after the hot water resistance test as shown in

Fig. 10. AMWFA had lower density than the standard sand,
suggesting the higher replacement ratio caused the lower
density value.
It was shown in Fig. 11 that the average pore diameter is in
the range of 0.10–0.14 mm, meaning it consisted of mainly
macro-pores regardless of the presence of AMWFA. The higher
replacement ratio of AMWFA caused increase in pore diameter.
The larger entraining air content due to the higher AMWFA
content could cause a slight increase in the pore diameter.

Fig. 12. SEM photographs of the specimens having the replacement ratio of AMWFA of 50% prior to (a–e) and after (f and g) the hot water resistance test: (a)
polymer cement modifier = 0%; (b) SBR polymer cement modifier = 10%; (c) SBR polymer cement modifier = 20%; (d) PAE polymer cement modifier = 10%; (e)
PAE polymer cement modifier = 20%; (f) SBR polymer cement modifier = 10%; (g) PAE polymer cement modifier = 10%.


E.-H. Hwang et al. / Journal of Industrial and Engineering Chemistry 14 (2008) 265–271

However, there was little difference in the average pore
diameter between different proportions of AMWFA after the
hot water resistance test.
3.7. Microstructure of the mortars
The microstructures of two specimens having SBR or PAE
polymer cement modifier of 10% and 20% with the replacement
ratio of AMWFA of 50% were observed by SEM prior to and
after the hot water resistance test (10% of polymer cement
modifier only), and shown in Fig. 12. In the presence of polymer

cement modifier, the components of mortar, cement hydrate,
AMWFA and polymer cement modifier were shown to stick to
each other, and present in the same co-matrix phase [29,35,36].
The remarkable shrinkage of polymer cement modifiers in the
mortar could be observed with the specimens after the hot water
resistance test due to the thermal degradation and deterioration of
polymer cement modifiers.
4. Conclusions
The effect of the type of polymer cement modifier in the
mortar using AMWFA was investigated and can be summarized
as follows.
(1) Adding polymer modifier into mortar reduced water–
cement ratio significantly. PAE was the more effective
polymer modifier to reduce water–cement ratio in this
mortar system than SBR.
(2) PAE emulsion-modified mortar increased the air content
entrained as the proportion of PAE was increased.
(3) There was little difference in water absorption between
SBR latex and PAE emulsion and it was decreased
drastically at 20% of polymer–cement ratio for both
SBR and PAE.
(4) The compressive strengths decreased in the presence of
polymer cement modifiers compared to that of no polymer
cement modifiers, but the compressive strength of 20% of
polymer–cement ratio was higher than that of 10%.
(5) After the hot water resistance test, both compressive
strength and flexural strength were decreased.
Acknowledgements
This study was supported by Ministry of Commerce,
Industry & Energy (MCIE) and Regional Innovation Center for

New Materials by Recycling (RIC/NMR) at Kongju National
University and here we would like to appreciate their supports.
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