Construction and Building Materials 47 (2013) 579–587

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Microstructures and mechanical properties of polymer modified mortars

under distinct mechanisms
Hongyan Ma, Zongjin Li ⇑
Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Hong Kong, China

h i g h l i g h t s

 Microstructures of polymer modified pastes are illustrated by a computer model.

 Effects of different polymer latexes on mechanical properties of mortar are revealed.
 Gel/space ratio is modified for polymer modified cement composites.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, two types of acrylic latexes, PA (polyacrylate) and PU/PA (polyurethane modified PA), are
Received 25 January 2013 investigated in their influences on mechanical properties of mortar under different interaction mecha-
Received in revised form 17 April 2013 nisms. In light of a previous study, the polymer–cement hydrates interaction mechanisms in PA and
Accepted 4 May 2013
PU/PA modified mortars are illustrated respectively, and the microstructures are simulated using a com-
Available online 8 June 2013
puter model. Through mechanical experiments, it is revealed that the incorporation of polymer tends to
reduce the compressive strength and elastic modulus except PA at low P/C ratio, while improve the flex-
Keywords:
ural strength and toughness. As compared with PA, PU/PA is more effective in these influences. All of the
Polymer modified mortar
PA
influences of PA and PU/PA on mechanical properties can be explained successfully based on the interac-
PU/PA tion mechanisms and microstructures. In addition, it’s also found that the compressive strength of poly-
Interaction mechanism mer modified mortar can be roughly estimated based on a modified gel/space ratio, and the incorporation
Mechanical properties of polymers does not change the relationship between elastic modulus and compressive strength. A high-
temperature curing procedure is concluded to be suitable for preparation of high-performance cement
composites in short period.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction In polymers that are commonly used for modification of ce-

In the last half century, polymer modified mortar and concrete
have been widely utilized in construction practice, as polymer
modification can improve the workability, adhesive strength,
waterproofness and many other properties of cement based mate-
rials [1–4]. Although polymer modified mortar and concrete are
mainly used as finishing or repair materials in their history [3], fol-
lowing the development of polymerization and composition tech-
niques, they have been sometimes used massively as the major
construction material in some projects, e.g. pavement [5]. In such
applications, polymer modification may be expected to increase
the tensile or flexural strength and toughness of the cement-based
materials, without inducing severe decrease in compressive
strength.
⇑ Corresponding author. Tel.: +852 2358 8751; fax: +852 2358 1534.
E-mail addresses: mhy1103@gmail.com (H. Ma), zongjin@ust.hk (Z. Li).
ment-based materials, in forms of latex, emulsion or re-dispersible
powder, SBR (styrene butadiene rubber), EVA (ethylene–vinyl ace-
tate copolymer) and acrylics have been deeply studied and broadly
utilized in practice [2,3,6–8]. In hardened state, the phenomena of
noticeable increase in flexural strength and no improvement or
even reduction of compressive strength of polymer modified
cement-based composites, as compared with unmodified ones,
have been commonly reported [3,4,9]. Of course, there are a lot
of different and even contrary reports, e.g. Pei et al. [10] found that
the incorporation of polymer latex negatively influence both
compressive and flexural strength; Mohammed et al. [11] reported
that waste latex paint modification with low P/C (polymer to ce-
ment mass ratio) might be positive in improving compressive
strength of concrete. Actually, results from the literature cannot
be compared with each other directly, if one does not recognize
that polymers are generally added into cement composites in
two different ways, say, keeping constant W/C (water to cement
ratio) to obtain similar hydration of cement and keeping constant

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.05.048
580 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587
consistency by adjusting the W/C or the inclusion of plasticizer
[12,13]. The former is a typical laboratory procedure, while the la-
ter is a trial-and-error procedure with its results directly applicable
in practice. Generally, significant improvements of flexural
strength were reported in studies using the later method. Barlu-
enga and Hernández-Olivares [12] noted that with SBR latex mod-
ification, keeping constant W/C, resulted in constant flexural
strength and noticeably decreased compressive strength, while
keeping constant consistency led to constant compressive strength
and significantly increased flexural strength.
In a recent study, the advantages and disadvantages of different
types of polymers, as modifiers of cement composites, were intro-
duced [14], through which it can be seen that acrylics have perfect
mechanical properties and durability. They are indeed frequently
employed in flooring compounds and mortars where the highest
level of physical performance (adhesion, abrasion resistance, flex-
ural strength, and impermeability) is required [2,6]. Compared
with SBR, acrylics as modifier can improve flexural strength more
significantly at the same P/C, and may not reduce the compressive
strength at low P/C [15]. The purpose of the present study is right
to modify cement mortar using acrylic latexes, and improve the
flexural strength and toughness without reducing compressive
strength obviously.
Mechanisms of the interaction between organic and inorganic
phases in acrylics modified mortars have been discussed in the
previous study [14]. Two types of acrylic latexes were used as
modifiers. One was polymerized by emulsion polymerization with
monomers of MMA (methyl methacrylate), AA (acrylic acid), HEMA
(2-hydroxyethyl methacrylate) and cross-linking agent. It was la-
beled as PA (polyacrylate). The other one was PU/PA (polyurethane
modified PA). In the present study, the interaction mechanisms are
introduced firstly. Then, the microstructure evolution of polymer
modified cement pastes are simulated using a status-oriented
computer model based on the interaction mechanisms. Keeping
constant W/C, influences of PA and PU/PA latexes on mechanical
properties of mortars are investigated experimentally, and ex-
plained based on the interaction mechanisms and simulated
microstructures.
2. Materials and experiments
PA and PU/PA latexes were used as polymer modifiers. The details of the synthe-
ses and physical properties of them can be found in the previous work [14]. Cement
that satisfies the requirements of BS EN197-1:2000 for CEM I Portland cement of
strength class 52.5N (roughly equivalent to the requirements of ASTM C150 for
Type I Portland cement) was used as binder. The chemical compositions and phys-
ical properties of the cement are listed in Tables 1 and 2, respectively. Siliceous sand
was used for preparing mortars with and without polymer. The fineness modulus of
the sand is 1.73, while the average and maximum grain sizes of the sand are
0.33 mm and 2.36 mm respectively. Deionized water was used for mixing various
mixtures. Besides, in the mixing process of polymer modified mixtures, a type of
organosilicon defoamer in proper amount was added to suppress the foaming effect
of surfactants in the latexes.
In the preparation of all mortars, with and without polymer, the W/C ratio was
kept 0.5, while the sand to cement weight ratio (S/C) was kept 2. Various P/C ratios
were selected to investigate its influence on mechanical properties. The mix propor-
tions of these mixtures are listed in Table 3. After mixing, the mixtures were cast in
steel moulds with different sizes for different test purpose. The size of specimen is
50 mm  50 mm  50 mm for compression test, 40 mm  40 mm  160 mm for
flexural test, and 25 mm  25 mm  160 mm for fracture energy test. After casting,
the mixtures were covered with plastic sheets to avoid evaporation. After 24 h, all
specimens were demoulded and cured according to three different procedures. Pro-
cedure 1 was a simple wet curing in a moisture room where the temperature and
Table 1
Chemical composition (%) of cement.
SiO2 Al2O3 Fe2O3 CaO MgO SO3 Loss on ignition
21.1 5.6 3.4 65.3 1.6 2.1 0.85
relative humidity were approximately 23 °C and 95% respectively. Procedure 2 con-
sisted of a 2-day wet curing and a following dry curing in ambient environment
(22 ± 2 °C and 40–70% RH). In procedure 3, a 2-day steam curing at 60 °C was fol-
lowed by a 4-day oven-drying at 60 °C and subsequently a dry curing in ambient
environment. Procedure 1 is the most beneficial to cement hydration, and thus to
the evolution of mechanical properties of unmodified mortars. Procedure 2 is a
commonly adopted method for polymer modified mortars as the dry curing is be-
lieved to be necessary for polymer film formation [3]. Procedure 3 is similar to
the one that was used to prepare a high flexural strength cement paste, in which
the steam curing and oven drying were used to promote cement hydration and film
formation respectively in short stages [16].
Mechanical tests were conducted at ages of 3, 7, 28 and 60 days. Compressive
strengths of mortars were measured according to ASTM C109, on a MTS 815 ROCK
Mechanics machine. Flexural strengths were tested using three-point bending on a
MTS 858 Mini machine, and calculated as
3P p L
ff ¼ 2
ð1Þ
2bt
where ff represents flexural strength, Pp the peak load, L (140 mm) the span of spec-
imen, b (40 mm) and t (40 mm) the width and height of the cross-section of the spec-
imen respectively. Elastic moduli of mortars were estimated from the load–
displacement curves of three-point bending according to the following equation,
L3 dP
E¼ 3
 ð2Þ
4bt dd
where dP/dd is the gradient of the load–displacement curve corrected for the small
amount of distortion in the three-point loading system. As this was not a standard
method, the results could not be compared with the data in the literature. Thus, only
the relative values of elastic moduli Er, i.e. the values after being normalized by the
elastic modulus of the reference mortar MPC at 60 days, would be shown in the pres-
ent paper. The fracture energy GF of mortars were roughly determined using a sim-
plified method. This method imitated the draft recommendation proposed by RILEM
Committee on Fracture Mechanics of Concrete-Test Methods [17] based on the ficti-
tious crack model. Small-size specimens that could not fulfill the recommendation
were used, and the notch length was equal to half depth of the beam. It must be
noted that GF measured in this way may not be the true values, thus they can only
be used to compare with each other, rather than with other data in the literature.
3. Latex-hydrates interaction mechanisms and microstructure
evolution
3.1. Interaction mechnisms of different types of polymer latices and
cement hydrates
The interaction mechanisms of the two different types of la-
texes (PA and PU/PA) and cement hydrates have been studied in
a previous work [14]. It has been found that after being incorpo-
rated into cement paste, PA latex is destabilized and demulsified.
PA molecules react with cement hydrates chemically to form a
compound rather than form high purity film. On the other hand,
PU/PA latex is just slightly demulsified, and still forms film with
high purity. Behaviors and properties of PU/PA latex modified paste
or mortar can be explained by Ohama’s multi-step model [3] to a
large extent, as PU/PA latex is sterically stabilized and PU/PA mol-
ecules are relatively passive. Behaviors of PA latex modified ce-
ment composites have to be explained by the newly developed
4-step model [14]. In step 1, immediately after mixing, a large
amount of polymer particles adsorb on the surface of cement par-
ticles or coalesce because of the demulsification. The rest are still
dispersed in the aqueous phase. Adsorption happens in mixing
process and the first several minutes after mixing. In step 2, the
hydration of cement is successively governed by dissolving and
migration of ions. Some chemical reactions take place between la-
tex and cement hydrates. Polymer particles adsorbed on the sur-
face of cement particles are partially or totally embedded in
hydrates. This stage lasts for tens of minutes until flocculation
occurs. In step 3, cement hydration further progresses. With the
reaction between calcium hydroxide and surfactant, the dispersion
is severely destabilized. Polymer particles with cement hydrates
settle down together, and flocculation happens. Due to the porous
nature of the flocs, the growth or sedimentation of hydrates and
the chemical reactions can continue in it, so that a complex
 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587 581

Table 2
Physical properties of cement.

Specific gravity Blain specific surface area (cm2/g) Setting time (min) Compressive strength (MPa)
Initial Final 2 days 7 days 28 days
3.15 3580 150 180 24.1 40.7 56.9

Table 3
Mix proportions of mortars in weigh ratio.
Mark Water Cement Sand Polymer solid weight
PA
MPC – –
MA05 0.05
MA10 0.1
MUA05 0.5 1 2 – 0.05
MUA08
MUA10
MUA15
MUA20
compound of cement hydrates and flocculated PA particles are
formed. Roughly speaking, this stage ends after wet curing ends.
At last in step 4, with the drainage of water, in a few spaces, poly-
mer film forms, but rarely and not continuously. More general sit-
uation is the formation of an organic–inorganic co-matrix.
3.2. Simulation of the microstructural evolution of latex modified
cement pastes
Based on the latex-hydrates interaction mechanisms introduced
above, in light of a status-oriented computer model for cement
hydration (details can be found in Refs. [18,19]), the microstruc-
ture evolution of polymer latex modified cement paste can be sim-
ulated. According to the status-oriented computer model, once W/
C and particle size distribution of cement are fixed, the microstruc-
ture of cement paste can be simulated as a function of degree of
hydration. The simulated microstructure is composed of anhy-
drous cement grains, inner hydrates layers, outer hydrates layers
and large capillary pores. The initial microstructure of polymer
modified cement paste can be simulated through randomly replac-
ing capillary water voxels by polymer voxels until the polymer vol-
ume fraction calculated from P/C is achieved. One polymer voxel is
used to simulate one polymer particle. In Fig. 1, the initial states of
pure cement paste (W/C = 0.5) and polymer modified cement paste
(W/C = 0.5, P/C = 0.1) are compared. In the figures, white, dark and
magenta represent cement particle, capillary water and polymer
particles respectively. The term ‘initial state’ means an assumed
PU/PA special state occurs immediately after mixing and before any
chemical reaction happens, thus PA and PU/PA modified pastes
need not to be distinguished from each other. At this state, polymer
particles are still uniformly dispersed in aqueous, just like in the
polymer latex. Keeping the same W/C, in the polymer modified ce-
0.08
0.1
ment paste, the volume fraction of cement is lower than that in
0.15 pure cement paste due to the incorporation of polymer. Note that
0.2 all two-dimensional images shown below are cross-sectional views
cut from the simulated three-dimensional microstructure.
The evolution of the microstructure of pure cement paste is
shown in Fig. 2, in which white, blue, green and dark represent
anhydrous cement grain, inner hydrates layer, outer hydrates layer
and large capillary pore respectively. Fig. 2a shows the state at the
age of 3 days, which is the end of wet curing. Fig. 2b shows the
state at 28 days when the paste is under air-dry curing and has
been relatively mature.
It is assumed that the incorporation of polymer latex in cement
paste does not influence the microstructure of inner hydrates layer,
but only significantly influence the microstructure of outer hy-
drates layer. To simulate the microstructure evolution of polymer
latex modified cement paste, irrespective of the type of latex, the
outer hydrates layer is divided into two layers, i.e. the compound
layer and the composite layer formed in two individual processes.
The compound layer is formed in the wet curing period under the
reaction between cement hydrates and the adsorbed polymer par-
ticles. The volume fraction of the compound layer can be easily cal-
culated based on the degree of hydration of cement and the
adsorption ratio of polymer, and the formation of this layer con-
tacting with the original surfaces of cement particles can be then
simulated according to the algorithm as described in Refs.
[18,19]. Polymer voxels in this layer are dispersed as they cannot
form any polymer film due to the chemical reactions. The
composite layer is formed following the withdraw of water and
the formation of polymer films. It is a composite of cement
hydrates and polymer films. The volume fraction calculation and

Fig. 1. Initial states of pure and polymer latex modified cement pastes (100 lm  100 lm): (a) pure cement paste (W/C = 0.5); (b) polymer latex modified cement paste (W/
C = 0.5, P/C = 0.1).
582 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587
Fig. 2. Microstructure evolution of pure cement paste (W/C = 0.5, 100 lm  100 lm): (a) 3 days; (b) 28 days.
overall formation simulation of this layer are similar with that of
the compound layer. Continuous polymer film in this layer can
be simulated by adding polymer voxels adhering to randomly
determined seed polymer voxels or existed polymer film voxels
until the volume fraction is achieved.
The microstructure evolution of PA modified cement paste is
shown in Fig. 3, while that of PU/PA modified cement paste in
Fig. 4. In these two figures, green and yellow are used to indicate
the cement hydrates in the compound layer and composite layer,
respectively, while magenta still the polymer phase. In the simula-
tions, it is assumed that the degree of hydration of cement in poly-
mer modified pastes are the same as that in pure cement paste at
the same age, as it has been proved experimentally that the incor-
poration of polymer latex only retards early hydration (especially
in the first day), but influences little on long-term hydration [20].
It can be seen that, regardless of the type of paste, the micro-
structure consists of several layers. Hydrated pure cement paste
contains four layers, i.e. anhydrous cement grain, inner hydrates
layer, outer hydrates layer, and large capillary pore layer. Under
the effects of polymers, the outer hydrates layer of polymer mod-
ified cement paste can be divided into two sub-layers, i.e. com-
pound layer and composite layer. The compound layer is mainly
formed by the organic–inorganic compound in the wet curing per-
iod as described above, while the composite layer is a cement hy-
drates-polymer film interpenetrated structure formed following
the withdraw of water in the dry curing period. It is obvious that
PA modified paste has relatively large volume of compound layer
due to the high adsorption ratio of PA, higher than 70%, compared
with lower than 20% of PU/PA [14], while PU/PA modified paste has
large volume of composite layer at comparable degree of hydra-
Fig. 3. Microstructure evolution of PA cement paste (W/C = 0.5, P/C = 0.1, 100 lm  100 lm): (a) 3 days; (b) 28 days.
tion. Besides, the much higher volume fraction of polymer in com-
posite layer of PU/PA modified paste guarantees that the formed
polymer network is continuous and interpenetrate with cement
hydrates. The microstructural differences between these two dif-
ferent types of polymer modified pastes are shown more clearly
in Fig. 5, in which Figs. 3b and 4b are locally zoomed in and com-
pared. Incorporation of polymer latex can improve the flexural
strength of cement composites because of the formation of contin-
uous polymer network which is interpenetrated with cement hy-
drates, as well as the constrain of polymer on skin and inner
micro-cracks [21]. Both PA and PU/PA are effective for the later
mechanism. As a continuous polymer network can form and inter-
penetrate with cement hydrates in the composite layer of PU/PA
modified paste, the PU/PA latex should be more effective in
increasing the flexural strength of mortar. Generally, incorporation
of polymer reduces the compressive strength, as polymer can be
considered as pore phase in the cement composite to a certain de-
gree [9], while to what a degree depends on the type of polymer.
4. Experimental results
4.1. Compressive strength
4.1.1. Influence of curing method on cement hydration and
compressive strength
It has been mentioned in Section 2 that three different curing
procedures were adopted for different purpose. Cement degree of
hydration and compressive strength evolution of un-modified
mortar cured under different procedures are shown in Fig. 6. The
 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587
Fig. 4. Microstructure evolution of PU/PA cement paste (W/C = 0.5, P/C = 0.1, 100 lm  100 lm): (a) 3 days; (b) 28 days.
Fig. 5. Microstructural comparison of different types of polymer modified pastes (W/C = 0.5, P/C = 0.1, 50 lm  50 lm): (a) PA modified paste, magnified from Fig. 3b; (b) PU/
PA modified paste, magnified from Fig. 4b.
evolutions of hydration degree of the cement (at W/C of 0.5) under
20 °C and 60 °C (isothermal) are from simulations using Hymostruc
developed in TU Delft. Note that these are rough simulations, as
only temperature is considered while the influence of the relative
humidity under different curing conditions cannot, due to the lim-
itations of the software. However, the accuracy of the simulation
result is enough for comparison purpose rather than accurate cal-
culation. It can be seen from Fig. 6 that the development of com-
Fig. 6. Influence of curing method on hydration and compressive strength
development of un-modified mortar.
583
pressive strength is directly related to degree of hydration. Due
to the high temperature, degree of hydration of cement at 3 days
under 60 °C reaches the level of that at 28 days under 20 °C. Thus,
the compressive strength of mortar cured by procedure 3 reaches a
mature level at very early age. That is why Bracknbury et al. [16]
used such a method to get high maturity in a short stage. The dif-
ference of compressive strength developments following proce-
dure 1 and procedure 2 can be attributed to the availability of
water for continuous hydration.
4.1.2. Influence of polymer on compressive strength
Although the wet curing is beneficial to cement hydration, and
the high temperature treating can promote hydration in a short
period and get high maturity fast, the wet plus air dry curing fol-
lowing procedure 2 is the most similar with that in practice. Thus,
more attention focuses on the comparison of unmodified mortar
MPC and polymer modified mortars cured by procedure 2. Follow-
ing curing procedure 2, the influence of polymers on the evolution
of compressive strength is shown in Fig. 7. Fig. 7a shows that the
incorporation of PA at the P/C of 0.05 (MA05) increases the com-
pressive strength at each age, but higher incorporation ratio leads
to the reduction of compressive strength. In Fig. 7b, it can be seen
that the incorporation of PU/PA tends to reduce the compressive
strength of mortar, and the higher the P/C, the larger the reduction,
except MUA08 at early ages.
According to Neville [22], regardless of age and aggregate
volume fraction, the compressive strength of concrete is directly
584 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587
proportional to the cube of the gel/space ratio, r, and can be calcu-
lated as
fc ¼ 234  r 3
where fc is the compressive strength in MPa, the 234 MPa is the
intrinsic strength of the hydrates gel of cement, and the gel/space
ratio, r, is defined as the ratio of the volume of cement hydrates
to the sum of the volumes of hydrated cement and of the original
capillary pores, i.e.
jh v c a
r¼
v c a þ W=C
where jh is the hydrates volume expansion factor of ordinary Port-
land cement, which indicates the volume of hydrates generated
when 1 unit volume of cement is completely hydrated. jh equals
to 2.13 according to Sanahuja et al. [23]. v c is specific volume of ce-
ment with the value 0.317 cm3/g. a is the degree of hydration of ce-
ment. Generally, the validity of this model is good in predicting
compressive strength of cement composite without polymer, as
shown in Fig. 8, giving that the cement degree of hydration equals
to 0.48, 0.54, 0.58 and 0.60 at the ages of 3, 7, 28 and 60 days,
respectively, as determined using the thermogravimetric method
described in Ref. [19]. The poor evolution of degree of hydration
at late ages should be attributed to the dry curing condition in
the corresponding period. Due to the soft nature of polymers
compared with cement hydrates, rather than aggregate which is
much more rigid and strong, polymer phase should be considered
Fig. 7. Influence of polymer modifications on the evolution of compressive
strength: (a) PA modified mortars vs MPC; (b) PU/PA modified mortars vs MPC.
as space to a certain degree. Thus, the gel/space ratio in polymer
modified cement composite should be modified to
ð3Þ jh v c a
r¼ ð5Þ
v c a þ W=C þ g  P=C
q P
where qP is the density of polymer, and g is the effectiveness coef-
ficient, which indicates to what a degree the polymer can be consid-
ered as space.
Experimentally determined compressive strengths of mortars,
ð4Þ
as a function of polymer type and P/C, have been plotted in
Fig. 9. Assuming g = 0, which means treating polymer as aggregate
with much higher rigidity, the predicted results according to Eqs.
(3) and (5) keep constant rather than a function of P/C. Assuming
g = 1, which means totally treating polymer as space and makes
the predicted results much lower than experimental values. By fit-
ting experimental results to Eqs. (3) and (5), it is found that
g = 0.502 for PU/PA and g = 0.257 for PA give the best fitting
respectively. PU/PA has higher effectiveness coefficient because
its rigidity is lower than PA, thus can be treated as space, or pore
to a higher degree. To sum up the above analysis, when studying
compressive strength of polymer modified cement composite,
polymer phase can be treated as space to a certain degree, while
to what a degree depends on the type, or rigidity of the polymer.
It must be noted that this theory has a presupposition, i.e. only
physical interactions occur between the polymer phase and ce-
ment hydrates, e.g. the effect of SBR latex on compressive strength
of cementitious materials [24]. According to this theory, the com-
pressive strength decreases with the increasing of P/C undoubt-
edly. However, the mortar MA05 gives an obvious exception, and
this may be attributed to the chemical reactions, as described in
the previous study [14]. In a low dosage of polymer addition, the
chemical reactions may make cement hydrates bond to each other
to form denser and stronger structure, which enhances the com-
pressive strength of polymer modified mortars. While in a high
dosage of incorporation, the polymer phase tends to form larger
particles which act as defects or partial spaces as described by
Eq. (5). Thus, there should be a threshold P/C, below which PA en-
hances compressive strength mainly under the chemical mecha-
nism, while above which the big grouping effect of PA will
exceed its positive effect so that the compressive strength can be
roughly estimated according to Eqs. (3) and (5). By a simple obser-
vation on the experimental results, this threshold P/C for PA should
be between 0.05 and 0.1. In another research which kept constant
W/C, the incorporation of a polyacrylate at low P/C was also
reported to improve the compressive strength [25].
Fig. 8. Experimentally determined compressive strength of MPC cured by proce-
dure 2 and predicted results by Eqs. (3) and (5).
 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587 585

Fig. 9. Influence of polymer on compressive strength at 28 days.

4.2. Flexural strength

The evolutions of flexural strength of mortars listed in Table 3,

cured following procedure 2 are plotted in Fig. 10. An initial anal-
ysis of the data leads to the following remarks regarding the influ-
ence of polymer. First, at the age as early as 3 days, the flexural
strength of almost all polymer modified mortars, irrespective of
the type of polymer and P/C ratio, are lower than that of MPC. This
is because the incorporation of polymer retards the early hydration
of cement on the one hand, and the polymer cannot form film in
the wet curing environment on the other. Second, at late ages,
e.g. 28 days and 60 days, following the withdraw of water and
the gradual formation of polymer film, polymers tend to increase
the flexural strength, especially for the cases with P/C from 0.05
to 0.1. PU/PA modifications with P/C > 0.1 seem to be not so effec-
tive in improving flexural strength, perhaps because the over-per- Fig. 10. Influence of polymer modifications on the evolution of flexural strength:
(a) PA modified mortars vs MPC; (b) PU/PA modified mortars vs MPC.
colation of polymer film is harmful to the continuity of cement
hydrates. Actually this is also true for PA modified mortars accord-
ing to limited data involving high polymer content. 4.3. Elastic modulus
Although no continuous film network can form in PA modified
mortars as shown in Fig. 3, PA can also improve the flexural Due to the reasons described in Section 2, only relative elastic
strength, as the incorporation of PA latex can effectively limit the moduli of mortars are plotted against age in Fig. 12. Simple obser-
formation of micro-cracks and delay the propagation of micro- vation can lead to a conclusion that the incorporation of polymer
cracks when loaded. Beside this mechanism, continuous polymer tends to decrease the elastic modulus of mortar, and the higher
film network can form in PU/PA modified mortars, as shown in the P/C, the larger degree of the decreasing at late ages. This is
Fig. 4, which helps to improve the flexural strength more signifi- almost a general feature of polymer modified cement composites,
cantly. E.g. at the age of 60 days, MA05 has a flexural strength of especially in the cases of keeping constant W/C [3,20,26].
8.51 MPa, which is 7.59% higher than the 7.91 MPa of MPC, while
the value of PU/PA modified mortar (MUA05) at the same P/C
and the same age is 9.68 MPa, which is 22.38% higher than MPC.
The data in Fig. 10 clearly highlight an optimum of polymer con-
tent, corresponding to P/C between 0.05 and 0.1 irrespective of
polymer type, with regard to improving flexural strength. A similar
conclusion has also been drawn by Bureau et al. [13] in their study
on mechanical properties of SBR modified mortars.
As compared with the mortars cured by procedure 2, the high-
temperature treated mortars following procedure 3 seem to have
higher flexural strength at the age of 28 days, as shown in
Fig. 11. The high-temperature steam curing not only promotes
the early hydration and generates more hydrates fast as proved
by Fig. 6, but also makes sure the high continuity of hydrates phase
at the end of 3 days. Under the help of the followed oven curing,
polymer film can form with high quality and without disturbing
the continuity of the hydrates phase. With these mechanisms,
PU/PA modifications even with high P/C ratio (0.2) can also im- Fig. 11. Flexural strength comparison of PU/PA modified mortars cured by different
prove the flexural strength. methods at the age of 28 days.
586 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587

Compared with others, the MA05 only has limited decreasing in

elastic modulus. Again, this may be attributed to the chemical
interactions between PA latex and cement hydrates.
According to the ACI building code (ACI 318), the elastic modu-
lus of concrete can be estimated using a binary function of its unit
weight and compressive strength. Assuming a constant density for
normal weight concrete, the elastic modulus will be directly pro-
portional to the square root of compressive strength [27]. Other
standards may use different equations to link elastic modulus to
compressive strength, e.g. in Eurocode 2 and CEB-FIP Model Code
the elastic modulus of concrete is directly proportional to the cubic
root of its compressive strength [28]. Although only relative elastic
moduli are given in the present study, it should also read

Er ¼ k1  fc1=2
or
Er ¼ k2  fc1=3
where k1 and k2 are constants. In Fig. 13, the elastic moduli of all
modified and unmodified mortars at different ages are plotted
against the corresponding compressive strength, and then fitted
using Eq. (6). It is obvious that the relationship between relative
modulus and compressive strength can be fitted by a unique func-
tion, irrespective of the type of mortar. In other words, the empirical
equations used to estimate the elastic modulus of concrete based on
compressive strength can also be used for polymer modified con-
crete. Based on the digitized three-dimensional microstructure as
described in Section 3, in light of multi-scale micromechanics [29]
ð6Þ
Fig. 13. The relation between relative elastic modulus and compressive strength.
ð7Þ
or finite element methods [30], the elastic properties of polymer
modified cement composite may be predicted more accurately.
4.4. Toughness
The ratio of flexural strength to compressive strength (ff/fc) of a
cement composite is an important indicator of its toughness
[24,31]. Higher ff/fc indicates higher toughness. The toughness indi-
cators of all mortars at late ages are shown in Fig. 14. It can be seen
that the incorporation of polymer latexes of both types can im-
prove the toughness (indicator). The effect of PA is very limited
at low incorporation ratio (P/C = 0.05), but considerable somewhat
at higher P/C ratio (0.1). PU/PA seems to be more effective in
increasing the toughness indicator, due to the formation of contin-
uous polymer film network as shown in Fig. 4.
The fracture energy GF of PU/PA mortars have been roughly
measured, and the results are shown in Fig. 15. Cured following
procedure 2, the incorporation of PU/PA latex helps to improve
the fracture energy. When P/C is not larger than 0.1, the degree
of improvement increase with the increasing P/C. However, when
P/C > 0.1, the improvement becomes not so significant, due to the
disturbed hydrates continuity induced by the large volume of poly-
mer. This trend is consistent with that of toughness indicator, as
shown in Fig. 14. MUA10 (P/C = 0.1) gives the best performance
at 28 days, with an increasing of around 40% in fracture energy,
as compared with MPC (P/C = 0). High-temperature treatment fol-
lowing procedure 3 further improves fracture energy, as clearly
shown in Fig. 15. Under the help of high-temperature steam, large
amount of hydrates form in the first 3 days with high continuity,

Fig. 12. Influence of polymer modifications on the evolution of elastic modulus: (a)
PA modified mortars vs MPC; (b) PU/PA modified mortars vs MPC. Fig. 14. Toughness indicator comparison of mortars cured by procedure 2.
 H. Ma, Z. Li / Construction and Building Materials 47 (2013) 579–587
Fig. 15. Fracture energy of PU/PA modified mortars at 28 days cured by different
methods.
and in the following oven-curing for facilitating polymer film for-
mation, higher P/C results in higher fracture energy.
5. Conclusions
The following conclusions can be drawn from the present
study:
(1) PA and PU/PA modified mortars have different microstruc-
ture, due to their differences in modification mechanisms.
This has been clearly illustrated in the present study under
the help of a status-oriented computer model for micro-
structure simulation.
(2) Incorporation of polymer tends to reduce the compressive
strength of mortar. The compressive strength of polymer
modified mortars can be roughly estimated based on a mod-
ified gel/space ratio.
(3) Polymer modifications reduce the elastic modulus of mortar,
but do not influence the elastic modulus-compressive
strength relationship. Irrespective of the type of mortar, its
elastic modulus can be estimated based on a unique function
describing the relationship between elastic modulus and
compressive strength.
(4) Cured under procedure 2, a curing method similar with the
environment in practice or in situ curing, polymer modifica-
tions can improve the flextural strength and toughness, and
PU/PA performs better than PA due to the formation of high-
quality polymer film network. In PU/PA modified mortars,
the P/C range between 0.05 and 0.1 seems to be the most
reasonable considering both function and cost.
(5) Cured under the high-temperature procedure 3, which con-
sists of a cement hydration promotion period and a polymer
film formation facilitation period, the flexural strength and
fracture energy of PU/PA modified mortars can be further
improved. Thus, this method has the potential to be used
to prepare high-performance cement composites in short
period.
Acknowledgements
Financial supports from a China Basic Research Grant, Basic Re-
search on Environmentally Friendly Contemporary Concrete
587
(2009CB623200) and from Hong Kong RGC, Systematic studies on
magnesium phosphate cement-based concrete (615810) are grate-
fully acknowledged.
References
[1] Chandra S, Ohama Y. Polymers in concrete. Boca Raton, FL.: CRC Press; 1994.
[2] Miller M. Polymers in cementitious materials. Shawbury, UK: Rapra
Technology; 2005.
[3] Ohama Y. Handbook of polymer-modified concrete and mortars. Park Ridge,
NJ.: Noyes Publications; 1995.
[4] Ohama Y. Polymer-based admixtures. Cem Concr Compos 1998;20:189–212.
[5] Yao H, Liang N, Sun L, Meng J. The design of the polymer cement concrete
pavement and the analysis of test road. J Chongqing Jiaotong Univ
2005;24:83–7.
[6] ACI-Committee-548. Polymer-modified concrete, ACI 548.3R-03. Farmington
Hills, MI.: American Concrete Institute; 2003.
[7] Chung DD. Use of polymers for cement-based structural materials. J Mater Sci
2004;39:2973–8.
[8] Ramakrishnan V. Latex-modified concretes and mortars: synthesis of highway
practice. Washington DC: National Cooperative Highway Research Program
(NCHRP), Transportation Research Board; 1992.
[9] Schulze J, Killermann O. Long-term performance of redispersible powders in
mortars. Cem Concr Res 2001;31:357–62.
[10] Pei M, Kim W, Hyung W, Ango AJ, Soh Y. Effects of emulsifiers on properties of
poly(styrene–butyl acrylate) latex-modified mortars. Cem Concr Res
2002;32:837–41.
[11] Mohammed A, Nehdi M, Adawi A. Recycling waste latex paint in concrete with
added value. ACI Mater J 2008;105:367–74.
[12] Barluenga G, Hernández-Olivares F. SBR latex modified mortar rheology and
mechanical behaviour. Cem Concr Res 2004;34:527–35.
[13] Bureau L, Alliche A, Pilvin P, Pascal S. Mechanical characterization of a styrene–
butadiene modified mortar. Mater Sci Eng, A 2001;308:233–40.
[14] Ma H, Tian Y, Li Z. Interactions between organic and inorganic phases in PA-
and PU/PA-modified cement-based materials. J Mater Civ Eng
2011;23:1412–21.
[15] Wu K, Zhang D, Song J. Properties of polymer-modified cement mortar using
pre-enveloping method. Cem Concr Res 2002;32:425–9.
[16] Bracknbury WR, Grzeskowiak R, Reid NL, Lynn ME. Flexural strengths of
polymer modified cement pastes prepared by a novel curing process. Cem
Concr Res 1988;18:971–9.
[17] RILEM committee on fracture mechanics of concrete-test methods.
Determination of the fracture energy of mortar and concrete by means of
three-point bend tests on notched beams. Mater Struct 1985;18:285–90.
[18] Ma H, Li Z. Modeling cement paste at micro-scale. In: Choi CK, editor.
Proceedings of the 2011 world congress on advances in structural engineering
and mechanics, Seoul, Korea: Techno-Press; 2011. p. 992–1004.
[19] Ma H, Li Z. Realistic pore structure of Portland cement paste: experimental
study and numerical simulation. Comput Concr 2013;11:317–36.
[20] Odler I, Liang N. Properties and development of the microstructure in cement
pastes modified by a styrene–butadiene co-polymer. Adv Cem Res
2003;15:1–8.
[21] Pascal S, Alliche A, Pilvin P. Mechanical behaviour of polymer modified
mortars. Mater Sci Eng, A 2004;308:1–8.
[22] Neville AM. Properties of concrete. 4th and final ed. New York: J. Wiley; 1996.
[23] Sanahuja J, Dormieux L, Chanvillard G. Modelling elasticity of a hydrating
cement paste. Cem Concr Res 2007;37:1427–39.
[24] Wang R, Lackner R, Wang PM. Effect of styrene–butadiene rubber latex on
mechanical properties of cementitious materials highlighted by means of
nanoindentation. Strain 2011;47:117–26.
[25] Medeiros MH, Helene P, Selmo S. Influence of EVA and acrylate polymers on
some mechanical properties of cementitious repair mortars. Constr Build
Mater 2009;23:2527–33.
[26] Wong WG, Fang P, Pan JK. Dynamic properties impact toughness and
abrasiveness of polymer-modified pastes by using non-destructive tests.
Cem Concr Res 2003;33:1371–4.
[27] Mindess S, Young JF, Darwin D. Concrete. 2nd ed. Upper Saddle River, NJ.:
Prentice Hall; 2003.
[28] Noguchi T, Tomosawa F, Nemati KM, Chiaia BM, Fantilli AP. A practical
equation for elastic modulus of concrete. ACI Struct J 2009;106:690–6.
[29] Julien S, Luc D, Gilles C. Modelling elasticity of a hydrating cement paste. Cem
Concr Res 2007;37:1427–39.
[30] Koenders EA, Dolado JS, van Breugel K, Porro A. Nano to microlevel modeling of
cement-based materials. ACI Special Publ 2009;267:1–10.
[31] Wang R, Wang PM, Li XG. Physical and mechanical properties of styrene–
butadiene rubber emulsion modified cement mortars. Cem Concr Res
2005;35:900–6.