Construction and Building Materials 48 (2013) 628–635

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Construction and Building Materials

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Effect of polycarboxylate superplasticizers on large amounts of fly ash

cements
Mar Toledano-Prados a,1,2, Miriam Lorenzo-Pesqueira a,1, Belén González-Fonteboa b,⇑,1, Sindy Seara-Paz c,3
a
School of Civil Engineering, Material Science Area of the University of A Coruña, Spain
b
School of Civil Engineering, Department of Construction Technology of the University of A Coruña, Spain
c
School of Building Engineering, Department of Construction Technology of the University of A Coruña, Spain

h i g h l i g h t s

 Interaction polycarboxylate superplasticizer–cement with high porosity fly ash was studied.

 Liquid polycarboxylate (LPC) and solid polycarboxylate (SPC) were used.
 Both increase fluidity and decrease water demand of cement products.
 SPC mortars present the highest compressive strengths and lowest water absorption.
 The dose of 0.15% of SPC is the one that provides the best performance.

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

Article history: This study analyzes the interaction between polycarboxylate superplasticizers and cements with large
Received 22 January 2013 amounts of high porosity fly ash. The analysis was performed with two polycarboxylate superplasticizers:
Received in revised form 27 June 2013 a liquid commercial polycarboxylate with polyoxyethylene side chains (LPC) and an experimental solid
Accepted 21 July 2013
polycarboxylate (SPC).
Available online 15 August 2013
The conclusions confirm that the use of these types of superplasticizers improves cement behavior,
increasing fluidity and decreasing the water demand of cement products. LPC is slightly more effective
Keywords:
than SPC. With regard to hardened performance, SPC provides cement mortars with a denser structure
Cement
Cement paste
which leads to higher compressive strengths and lower water absorption capacity than in both mortars
Mortar containing cement without superplasticizer and the mortar with LPC. The best performance was had with
Polycarboxylate superplasticizers a dose of 0.15% SPC.
Fly ash Ó 2013 Elsevier Ltd. All rights reserved.
Solid superplasticizers

1. Introduction and objectives
The addition of mineral admixtures to Portland cement reduces
the amount of clinker, which serves to improve the environmental
efficiency of the manufacture process. Specifically, the addition of
pozzolanic materials such as natural pozzolans, fly ash, slag or sil-
ica fume to cement is considered to be beneficial, providing techni-
cal, economic and environmental improvements to the cement
products [1–6]. However, all of these pozzolanic materials may af-
⇑ Corresponding author. Address: E.T.S.I. Caminos, Canales, Puertos, Campus
Elviña s/n, 15071 La Coruña, Spain. Tel.: +34 981167000x1442; fax: +34 981167170.
E-mail addresses: mtoledano@udc.es (M. Toledano-Prados), bfonteboa@udc.es
(B. González-Fonteboa), gumersinda.spaz@udc.es (S. Seara-Paz).
1
Address: E.T.S.I. Caminos, Canales, Puertos, Campus Elviña s/n, 15071 La Coruña,
Spain.
2 For example, the specific surface area of the fly ash increases as
Tel.: +34 981167000x1453; fax: +34 981167170.
3
Address: E.U. Arquitectura Técnica, Campus Zapateira s/n, 15071 La Coruña,
Spain.
fect the water demand of cements as well as the interaction be-
tween superplasticizers and cements [7].
The use of fly ash is very common because it increases harden-
ing strength and improves durability (reducing alkali aggregate
reaction). When this addition is used, some considerations should
be taken into account [8]: (i) The density of fly ash is lower than
that of cement. Accordingly, if part of the cement is replaced with
fly ash by mass ratio, the paste volume of the mixture increases. (ii)
Fly ash prevents cement particles from forming into blocks. (iii) Fly
ash delays the hydration of cement. (iv) As fly ash is spherical in
shape, it has a ball-bearing effect.
Moreover, the improvement of the fluidity of pastes by the
addition of fly ash has been widely reported [9–14], reducing the
dose of superplasticizer needed. However, the fly ash collected in
each electrostatic precipitator hopper has different properties.
the collection hopper moves away from the boiler [15–17]. If fly
ash with different particle size distributions is added to the ce-

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.07.069
 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635 629

ment, the particle size distribution of the fly ash–cement system Table 1

changes, affecting the packing density of the pastes so that the Physical properties and chemical analysis of fly ash and clinker.

water retention of the pastes will vary. Thus, the fluidity of the Fly ash Clinker
pastes is expected to change [18–20], which indicates that fly Specific surface BET (m g2 1
) 15.6 (RV = 3.6) –
ash fineness determines the properties of the end material. Pore volume (cm3 g1) 0.0450 (RV = 0.019) –
The fresh characteristics of pastes, mortar or concretes made SiO2 (%) 52.66 20.28
with Portland cement can be modified in different ways: by using CaO (%) 6.89 65.07
Free CaO (%) 0.20 1.12
a high water to cement ratio or a water reducer admixture. Given Al2O3 (%) 23.41 5.49
the fact that an increase in the water to cement ratio causes Fe2O3 (%) 6.49 3.74
strength to decrease [21], the use of superplasticizers or water- SO3 (%) – 1.80
reducing chemical admixtures (WR) is closely linked to concrete K2O (%) – 1.04
MgO (%) – 2.08
technology.
Loss of ignition (%) 3.41 0.4
A wide variety of WR are commercially available nowadays.
Conventional superplasticizers such as naphthalene (PNS)-, mela- Note: RV: reference values [38–40].
mine (PMS)- or lignosulfonate (LS)-based disperse the particles
due to an electrosteric mechanism, while polycarboxylates (PCE)
2.1.2. Superplasticizer
form a steric obstacle to any direct inter-particle contact [22–26].
A solid polycarboxylate (SPC) and a liquid commercial polycarboxylate (LPC)
Comb-type additives consisting of a polycarboxylate backbone with a solid content of 33% were used as superplasticizers. Their physical and chem-
with polyoxyethylene side chains (PC-PEO) provide more diversity ical properties are shown in Table 3.
in their molecular architecture [27]. The length and density of PEO
chains as well as the molecular weight of the polymer can be ad-
2.1.3. Modified cements
justed to create additives with different performance characteris-
From the reference cement, four modified cements (MD), MD_SPC_0.05;
tics [28–31], and by modifying the bond structure between the MD_SPC_0.10; MD_SPC_0.15 and MD_SPC_0.20 with 0.05, 0.10, 0.15 and 0.20%
main backbone and side-chain, workability retention can be respectively of SPC, were made by mixing the dose of SPC with 5 kg of the RC.
manipulated [32]. The laboratory grinding mill was used for this purpose, operating at 15 rpm for 30s.
Achieving the greatest workability is contingent upon the com-
patibility between the admixture and the cement used [7]. The 2.1.4. Cement pastes
presence of mineral additions such as limestone, fly ash and silica The cement pastes were prepared by blending water with 500 g of the MD. Two
fume may affect the interaction between the superplasticizer and different types of cement pastes were made, one using a variable quantity of water
the cement. The performance of additions could also be influenced (MDv), which was required to achieve the normal consistency according to the
standard (UNE EN 196-3), and the other using a constant water/cement (w/c) ratio
by admixtures. The compatibility of mineral additions containing,
of 0.372 (MDc), which corresponds to the quantity of water that provides the nor-
and having an affinity for, a given admixture must therefore be mal consistency of the RC. Table 4 shows the different cement pastes used in this
determined [33–37]. work.
This study focused on the analysis of the interaction between
polycarboxylate superplasticizers and a cement with a large
2.1.5. Cement mortars
amount of a high porosity fly ash (cement type IV according to In the same way, two different types of mortar were made using the modified
the UNE EN 197-1), examining the effect on the behavior of cement cements (MDM). One type was prepared according to UNE-EN 196-1, which estab-
in the fresh and hardened states. In order to do so, two polycarbox- lishes a constant water to cement ratio (w/c = 0.50) (MDMc), and the other type, de-
ylate superplaticizers were used: a commercial polycarboxylate signed to quantify the effect of the SPC on water reduction, was made with a
variable water to cement ratio (MDMv). In this case the necessary amount of water
with polyoxethylene side chains PC-PEO and an experimental solid
was used to obtain a workability of 100–105% with the minislump test.
polycarboxylate. Moreover, in order to compare the behavior of the SPC with the commercial LPC,
another group of cement mortars were made using the reference cement. In this
case, the LPC was added to the mortars with the mixing water. Each cement mortar
made with SPC was compared with its corresponding cement mortar containing
2. Materials and tests LPC (with the same quantity of solid admixture). Tables 5 and 6 show the different
cement mortars used in this work with both additives, solid and liquid. In LPC mor-
2.1. Materials tars, the water present in the composition was taken into account, which leads to a
reduction in the water added during mix manufacturing.
The following materials were used in this research.

2.2. Test

2.1.1. Reference cement 2.2.1. Setting test

In order to produce the reference pozzolanic cement (RC), the materials, clinker,
fly ash and gypsum were ground at a proportion of 57:40:3 by mass in a laboratory
grinding mill employing spherical steel balls, ranging from 20 to 90 mm in diame-
ter, and running at 42 rpm during 90 min.
Table 1 shows the chemical characterization of the clinker and fly ash used in
this study determined by X-ray fluorescence. The pore volume and specific surface
of the fly ash determined with SORPTOMATIC 1990 (TermoQuest) equipment
(adsorption-desorption isotherms method) are also given in Table 1. Finally, Fig. 1
shows the image of the fly ash particles obtained by scanning electron microscopy
(SEM).
The fly ash met the requirements for type V cement according to UNE EN 197-1.
It is a heterogeneous material consisting of fine, spherical and mostly irregular par-
ticles. The pore volume and specific surface are higher than those of typical fly ash
[38–40], as can also be seen in Table 1 where reference values are given. These
properties are the ones mainly responsible for the high water demand leading to
the low workability of the cement.
Table 2 shows the physical properties of the RC that meets the requirements for
type IV cement according to UNE EN 197-1.
The setting times of cement pastes were determined using the Vicat needle test
method, according to standard UNE-EN 196-3.
2.2.2. Minislump test
Mortar flowability was measured using the minislump test according to stan-
dard UNE-EN 1015-3. Mortars were prepared at 20 °C and subsequently poured into
a truncated conical mold with the following measurements: upper diameter
70 ± 0.5 mm, bottom diameter 100 ± 0.5 mm and height 60 ± 0.5 mm. Flow area
(spread) was measured after 15 strokes, and also after 30, 60, 90, and 120 min of
mixing to evaluate the time dependent workability of the mortars. The spread
was the average of two perpendicularly crossing diameters. Using this value, a
spread ratio was calculated according to the following equation:
Spread ratio ð%Þ ¼ ðSpread  D0Þ  100=D0
where D0 = 100 mm is the bottom diameter and spread is the average of two perpen-
dicularly crossing diameters (mm).
630 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635

Fig. 1. SEM images of fly ash (a) 3500; and (b) 9000.

Table 2
Physical properties of reference cement (RC).
Table 6
Cement retained on 45 lm sieve (%) 10.0 Cement Mortars types with a variable water to cement ratio.
Cement retained on 32 lm sieve (%) 18.0
Cement mortars % Additive water to cement
Blaine fineness (cm2 g1) 3200
Specific gravity (g cm3) 2.84 RCMv 0 0.57
MDMv_SPC_0.05 0.05 0.55
Cement pastes water demand (%) 186
MDMv_LPC_0.05 0.15 0.55
Initial setting time (min) 305
MDMv_SPC_0.10 0.10 0.54
Final setting time (min) 330
MDMv_LPC_0.10 0.30 0.53
Cement mortar MDMv_SPC_0.15 0.15 0.51
Spreading (%) 40 MDMv_LPC_0.15 0.45 0.50
MDMv_SPC_0.20 0.20 0.49
MDMv_LPC_0.20 0.60 0.47

2.2.3. Hardened behavior of cement mortars

Table 3
The compressive strength of cement mortars was determined according to stan-
Properties of the additives.
dard UNE-EN 196-1. In addition, a scanning electron microscopy image of the mor-
SPC LPC tar fracture surface was taken after 28 days. Images obtained at 20 can
qualitatively describe the pore structure in order to establish its influence on the
Colour White Yellow compressive strength of mortars.
Solid content (%) 100 33
C (%) 52.7 52.8
H (%) 9.6 8.3 3. Results and discussion
pH 6 4.5
Density (g/cm3) 1.03 1.08
3.1. Cement pastes with a constant w/c ratio. Setting time

The setting of cement is a percolation process in which isolated

Table 4 or weakly bound particles are connected by the formation of
Cement pastes types. hydration products. The water to cement ratio has a strong influ-
Cement pastes % Additive Water (ml) Water to cement ence on the setting time, as higher w/c pastes will require more
hydration time and will likely take longer to achieve set due to
RC 0 186 0.372
MDv_SPC_0.05 0.05 185 0.370 the larger initial particle spacing [41–43]. Also the use of some
MDc_SPC_0.05 186 0.372 types of superplasticizers (including the polycarboxylate and
MDv_SPC_0.10 0.10 184 0.368 naphthalene sulfonates) retards the setting time of cement pastes.
MDc_SPC_0.10 186 0.372 There are well known explanations (chemical and physical) to this
MDv_SPC_0.15 0.15 181 0.362
effect, such as electrostatic repulsion, the steric hindrance effect as
MDc_SPC_0.15 186 0.372
MDv_SPC_0.20 0.20 178 0.356 a result of side chains of the polymer adsorbed on cement particles,
MDc_SPC_0.20 186 0.372 and greater dispersion of cement particles which impedes the for-
mation of localized agglomerates [27,47,48].
Fig. 2 shows the results obtained over time using the Vicat nee-
dle test and cement pastes with a constant water to cement ratio.
Table 5
Cement Mortars types with a constant water to cement ratio.
As expected, with an increasing percentage of additive, the time
needed to achieve the penetration value of the reference cement
Cement mortars % Additive Water to cement
paste also increases. This means that there is an excess of water
RCMc 0 0.50 that increases with the additive dosage. Fig. 3 and Table 7 show
MDMc_SPC_0.05 0.05 0.50 the time needed to achieve a penetration value of 5 mm (initial set-
MDMc_LPC_0.05 0.15
MDMc_SPC_0.10 0.10 0.50
ting time). It is seen to increase with the percentage of SPC used,
MDMc_LPC_0.10 0.30 which agrees with the results of other researchers [28,44–46].
MDMc_SPC_0.15 0.15 0.50 Although the increases in setting time are usually noteworthy
MDMc_LPC_0.15 0.45 [45,46], this is not always the case, as evidenced in this paper (with
MDMc_SPC_0.20 0.20 0.50
0.20% of SPC, the setting time increased by 18.5%). In these cases,
MDMc_LPC_0.20 0.60
some researchers [32,44,45] have reported that it may be related
 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635 631

30
RC
25 MDc_SPC_0.05
MDc_SPC_0.10
Penetration (mm)

MDc_SPC_0.15
20
MDc_SPC_0.20

15

10

0
200 250 300 350 400 450
Time (min.)

Fig. 2. Penetration values according to the Vicat test vs time. Cement pastes with a
w/c ratio of 0.37.

20 Fig. 4. Chemical attack of an alkali group to carbonyl carbon of an ester molecule

[31].
18 y= 261.2903x2 + 36.5627x
16 R² = 0.9767
Time increment (%)

14 ash were used. Thus, it can be concluded that the high porosity of
12 the fly ash used in this work significantly increases the water de-
10 mand of the cement pastes. The use of the SPC in the modified ce-
8 ments decreases this water demand.
6 The plasticizing effect of the SPC is also shown in Fig. 5 (water
4 reduction vs% of solid polycarboxylate). It can be observed that
2
the water reduction increases with the percentage of SPC. An SPC
value of 0.2% of leads to a water reduction of 4.30%.
0
0 0.05 0.1 0.15 0.2 When the setting time of cement pastes with a variable water to
% of solid polycarboxylate cement ratio was studied, Fig. 6, it was observed that with values
of up to 0.1%, the initial and final setting times increased with
Fig. 3. Initial setting time vs SPC dosage. Cement pastes with a constant w/c ratio of the dosages of SPC. This trend, however, changed when 0.15%
0.37.
and 0.2% were examined, resulting in a decrease in times with
increasing SPC percentages. In these cases, the reduced water con-
Table 7
tent moderates the SPC effect, leading to this change in trend.
Setting time. Cement pastes with a constant water to cement ratio.

Cement pastes Initial Increment (%)

Table 8
RC 300 – Water demand and setting time. Cement pastes with a variable w/c ratio.
MDc_SPC_0.05 311.3 3.7
MDc_SPC_0.10 319.3 6.4 Setting time (min)
MDc_SPC_0.15 329.5 9.8 Cement pastes w (ml) wr (%) Initial Final Dt
MDc_SPC_0.20 355.5 18.7
RC 186 – 300 335 35
MDv_SPC_0.05 185 0.54 310 365 55
MDv_SPC_0.10 184 1.08 320 365 45
MDv_SPC_0.15 181 2.69 315 340 25
to the bond structure between the main chain backbone and the MDv_SPC_0.20 178 4.30 300 325 25
side-chains of copolymers of PC-based superplasticizers. Therefore,
when the side-chains are bonded to the main chain by an ‘‘ester’’
bond, it can easily lose its stability at alkali ambient owing to a
hydrolysis reaction as shown in Fig. 4. The number of attached
5
side-chains on the backbone is reduced by this reaction, which pro-
duces the corresponding alcohol and carboxylate compounds, 4.5

decreasing the effectiveness of the additive over time. 4 y = 90.184x2 + 3.6074x

Water reduction (%)

3.5 R² = 0.9946

3
3.2. Cement pastes with a variable w/c ratio. Setting time and water
demand 2.5

2
The water needed to achieve the normal consistency according 1.5
to standard (UNE EN 196-3) (w), water reduction (wr), calculated 1
taken into account the water demand of the RC, and the initial
0.5
and final setting times of the cement pastes with a variable w/c ra-
0
tio are shown in Table 8. 0 0.05 0.1 0.15 0.2
The amount of water required to obtain the standard consis- % of solid polycarboxylate
tency with the RC was higher than the amount needed when other
cements with the same composition but with another source of fly Fig. 5. Water reduction vs SPC dosage. Cement pastes with a variable w/c ratio.
632 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635

400 90
Final
80 SPC
350 Initial
LPc
70

Spread increment (%)

300
Setting time (min)

250 60
y = 1798.9x2 + 60.847x
50 R² = 0.995
200
40
150
30
100 y = 1059.9x2 + 99.539x
20 R² = 0.9897
50
10
0
0 0.05 0.1 0.15 0.2 0
0 0.05 0.1 0.15 0.2
% of solid polycarboxylate
% of polycarboxylate
Fig. 6. Setting time. Cement pastes with a variable w/c ratio.
Fig. 7. Workability vs superplasticizer dosage. Cement mortars with a w/c ratio of
0.50.

3.3. Cement mortars with a constant w/c ratio. Fluidity

cement and SPC is satisfactory, and does not present any opera-
As has been discussed, the SPC reduces the water demand in ce-
tional problems related to heterogeneity or poor adsorption of
ment pastes. The aim of this section is to assess the effect exerted
the additive over time.
by SPC on the water demand and fluidity of cement mortars. More-
However, the rate of reduction in flowability of the mortars
over, the behavior of the SPC has been compared with the behavior
with SPC is higher than that of the mortar with the reference ce-
of a commercial liquid superplastizer (LPC). The percentage of the
ment. Moreover, this loss of flowability mainly occurs during the
active group of the LPC, calculated with the dry weight, has been
first 60 min, when the spread ratio undergoes reductions of 60–
used to present the results.
75% compared to the initial values. It has also been detected that
As mentioned in Section 2.2, the fluidity of the standard cement
the rate of decrease rises with the percentage of SPC. The flowabil-
mortars with a constant water to cement ratio has been evaluated
ity of any of the modified mortars with SPC is always higher than
using the minislump test. The data obtained are shown in Table 9.
that of the reference mortar. The increases, quantified by the ratio:
It can be seen that the use of either superplasticizer (SPC or LPC)
‘‘experimental value of SPC mortars/experimental value of refer-
increases the fluidity, which agrees with the results obtained by
ence mortar’’, are 1.25, 1.63, 2.5 and 3.13 for MDMc_SPC_0.05,
other authors [45]. As the percentage of superplasticizer increases,
0.10, 0.15 and 0.20, respectively.
the spread ratio also rises.
When mortars with LPC are analyzed, it can be seen that, except
The relationship between the amount of superplasticizer (SPC
for the highest dosage of superplasticizer (LPC_0.20), the rate of de-
or LPC) and the spread ratio is shown in Fig. 7. With the data ob-
crease in flowability of these mortars is similar to that of the refer-
tained, the figure seems to shows a parabolic trend when using
ence mortar. Therefore, the loss of flowability of the mortars with
both SPC and LPC. Moreover, it can be seen that commercial LPC
SPC is higher than that of the mortars with LPC.
is slightly more effective than the SPC, with MDMc_LPC_0.20
Again, these data can be explained according to the results re-
showing a spread increment of 85.7% while MDMc_SPC_0.20 pre-
ported by other authors [32]. As mentioned earlier, when the
sents an increment of 60.7%.
side-chains of superplasticizers are bonded to the main-chain by
an ester bond, they lose their stability at alkali ambient due to
3.4. Time dependant flowability of the cement mortars hydrolysis reactions so, mortars do not increase setting times
and the rates of slump-flow loss are high.
In general it was confirmed that the additive used in this study
significantly improves the workability of the mortar after mixing
3.5. Cement mortars with a variable w/c ratio. Water demand
and the use of the SPC was found to be an effective tool in correct-
ing the deficiency of the rheological behavior of cement. However,
The quantity of water necessary to obtain a given workability of
it is necessary to determine the duration of the fluidity of the ce-
100–105% with the minislump test was quantified using the
ment and water system over time.
Fig. 8 shows the time dependant flowability of the cement mor-
tars with different dosages of SPC as well as with different dosages 180
of LPC. Fluidity can be seen to decrease gradually over time, and RC
160 MDMc_SPC_0.05
therefore it can be concluded that the mixing method between
MDMc_LPC_0.05
140
MDMc_SPC_0.10
Spread ratio (%)

120 MDMc_LPC_0.10
Table 9 MDMc_SPC_0.15
Spread ratio. Cement mortars with a constant w/c ratio. 100
MDMc_LPC_0.15
80 MDMc_SPC_0.20
Cement mortars Water to cement Spread ratio (%)
MDMc_LPC_0.20
RCMc 0.50 40 60
MDMc_SPC_0.05 0.50 50
40
MDMc_LPC_0.05 0.50 55
MDMc_SPC_0.10 0.50 65 20
MDMc_LPC_0.10 0.50 75
0
MDMc_SPC_0.15 0.50 100 0 20 40 60 80 100 120
MDMc_LPC_0.15 0.50 105
MDMc_SPC_0.20 0.50 125
Time (min)
MDMc_LPC_0.20 0.50 160
Fig. 8. Flowability vs Time (SPC and LPC). Cement mortars with a w/c ratio of 0.50.
 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635 633

different mortars. Again, in this case, the behavior of the mortars
with SPC has been compared with the behavior of the mortars with
the commercial liquid superplasticizer (LPC). The w/c ratio used for
each of the mortars is shown in Table 10. Fig. 9 shows the data re-
lated to water reduction percentage calculated with respect to the
RCMv.
The results agree with those obtained when standard mortars
with a constant water to cement ratio and when cement pastes
were analyzed. Both additives have a plasticizing effect acting as
effective water reducers. Moreover, it was observed that the
behavior of the SPC is similar to the behavior of the commercial
LPC. However, the use of the LPC was slightly more effective than
the use of SPC (Fig. 9).
The plasticizing effect of SPC, regardless of the dosage used, was
found to be higher in cement mortars than in cement pastes, which
agrees with the results obtained by other authors [45]. An SPC va-
increased with the SPC content mainly due to the decrease of the
water to cement ratio, as shown in Fig. 11. However, the mortar
with 0.15% SPC once again provided the highest compressive
strength at 60 days, even with a higher water to cement ratio than
0.20% SPC mortar.
All the mortars studied showed a similar time-dependent com-
pressive strength compared to the evolution of the reference
mortar.
It is thus noted that cement mortars made with 0.15% SPC pro-
vide a great many features for the constant and variable series.
After obtaining the suitable dosage of solid additive, 0.15%, LPC
mortars whit this percentage of additive were made in order to
58
53

Compressive strength (MPa)

lue of 0.2% leads to a water reduction value of 13.73% in cement
48
mortars while cement pastes underwent a water reduction of
4.3% for the same SPC dosage (Fig. 5). 43

38
3.6. Compressive strength of cement mortars with SPC 33 RCMc

28 MDMc_SPC_0.05
The effect of SPC content on the compressive strength of cement MDMc_SPC_0.10
mortars is an important feature to define proper dosage. For this 23
MDMc_SPC_0.15
reason, compressive strength at different ages was determined 18
MDMc_SPC_0.20
for SPC mortars and compared with the reference one. Figs. 10 13
and 11 show the compressive strength of the mortars at 2, 7, 28 0 10 20 30 40 50 60
and 60 days of age. Time (days)
The SPC cement mortars with a constant water to cement ratio
had a slightly higher compressive strength than the reference one Fig. 10. Compressive strength vs time. Cement mortars with a constant w/c ratio of
0.5.
at early ages, while at 28 and 60 days of age the values obtained
were similar to those of the reference mortar. Only the cement
mortar with a SPC content of 0.15% showed better behavior than
58
the reference mortar at any age (Fig. 10).
53
Compressive strength (MPa)

With a variable water to cement ratio, the compressive strength

48
Table 10
43
Water demand and spread ratio. Cement mortars with a variable w/c ratio.
38
Cement mortars Water to Water Water Spread ratio
cement (l) reduction (%) (%) 33 RCMv - w/c=0.57

RCMv 0.57 255 0 100 28 MDMv_SPC_0.05 - w/c=0.55

MDMv_SPC_0.05 0.55 248 2.75 105 MDMv_SPC_0.10 - w/c=0.54
23
MDMv_LPC_0.05 0.55 248 2.75 100
MDMv_SPC_0.15 - w/c=0.51
MDMv_SPC_0.10 0.54 240 5.88 100 18
MDMv_LPC_0.10 0.53 235 7.84 100 MDMv_SPC_0.20 - w/c=0.49
13
MDMv_SPC_0.15 0.51 227 10.98 105
0 10 20 30 40 50 60
MDMv_LPC_0.15 0.50 225 11.77 105
MDMv_SPC_0.20 0.49 220 13.73 105 Time (days)
MDMv_LPC_0.20 0.47 211 17.26 105
Fig. 11. Compressive strength vs time. Cement mortars with a variable w/c ratio.

20
SPC 58
18
LPC 53
Compressive strength (MPa)

16
Water reduction (%)

14 48
y = 134.09x2 + 59.481x
12 R² = 0.9966 43
10 38
8 y= 68.311x2 + 56.85x 33
6 R² = 0.99 MDMc_SPC_0.15 - w/c=0.50 - wabs=7.1%
28
MDMc_LPC_0.15 - w/c=0.50 - wabs=7.4%
4
23 MDMv_SPC_0.15 - w/c=0.51 - wabs=7.1%
2
18 MDMv_LPC_0.15 - w/c=0.50 - wabs=7.4%
0 RCMc - w/c=0.50 - wabs=7.3%
0 0.05 0.1 0.15 0.2 13
% of polycarboxylate 0 10 20 30 40 50 60
Time (days)
Fig. 9. Water reduction vs superplasticizer dosage. Cement mortars with a variable
w/c ratio. Fig. 12. Compressive strength vs time. Cement mortars with SPC and LPC.
634 M. Toledano-Prados et al. / Construction and Building Materials 48 (2013) 628–635
RC
382µm
2 mm
SPC_0.10 SPC_0.15
131µm
2 mm 2 mm
Fig. 13. Scanning electron images of mortar with SPC. Cement mortars with a constant w/c ratio.
compare the behavior of SPC with LPC in terms of compressive
strength. Moreover the water absorption capacity (wabs) of these
cement mortars was evaluated.
As shown in Fig. 12, SPC mortars experienced higher compres-
sive strength than LPC mortars, especially at 60 days of age. In this
case, LPC mortars (with constant, MDMc_LPC_0.15, and with vari-
able, MDMv_LPC_0.15, water to cement ratio) show practically the
same compressive strength values (which makes it impossible to
distinguish between the two lines in the figure). As explained ear-
lier, the water added during the mixing process was corrected in
order to take into account the water of the LPC additive.
As regards water absorption, mortars with 0.15% SPC had a low-
er value than that of the reference mortar, while mortars with LPC
were higher.
Using scanning electron microscope images (SEM, 20), the
pore size and the pore size distribution were observed. Fig. 13
shows the images of the SPC mortars and of the reference mortar
with a constant water to cement ratio at 28 days. These images
were used as a support to qualitatively explain the effect of differ-
ent percentages of SPC on the compressive strength. It can be seen
that the SPC mortars are more compact and present smaller pore
size than the reference mortar (Fig. 13), and as the percentage of
SPC increases a denser structure is obtained. The SPC mortar with
0.20% and 0.15% of additive shows the most compact structure,
which would justify increasing the compressive strength.
The results of these properties, compressive strength and water
absorption, indicate that the mortar with 0.15% SPC provides the
best performance.
4. Conclusions
The interaction between a solid and a liquid polycarboxylate
superplasticizer and a cement with a large amount of a high poros-
ity fly ash (cement type IV according to the UNE EN 197-1) was
investigated in this work, and according to the results obtained,
the following conclusions can be drawn:
 Setting time increases with the percentage of solid superplasti-
cizer [28,47,48]. However, the retarding effect was not as signif-
icant as usual, possibly due to a hydrolysis reaction also
detected by other authors [32,44,45].
SPC_0.05
160µm
2 mm
SPC_0.20
2 mm
 The use of either of the superplasticizers (solid or liquid)
increases the fluidity of the mortars. As the percentage of
superplasticizer increases, the spread ratio increases as well.
Moreover, it can be seen that the commercial LPC is slightly
more effective than the SPC. However, the rates of decrease in
flowability over time of SPC mortars are higher than that of both
the reference mortar and the LPC mortars. This may be due,
again, to the hydrolysis reaction.
 The use of SPC decreases the water demand, in both pastes and
mortars. Moreover, it can be seen that the behavior of the SPC is
similar to the behavior of the commercial LPC, with the LPC,
again, being slightly more effective than the SPC.
 The SPC gives a denser structure to cement mortars which leads
to higher compressive strengths and lower water absorption
capacity than both reference and LPC mortars.
 Finally, based on the analysis of all these properties it can be
concluded that, when only workability is taken into account,
the use of LPC provides a slightly better performance than the
use of SPC, and that an increase in the percentage of either
one up to 0.2% leads to an increase in workability. However,
when compressive strength is analyzed, the best performance
is obtained with the use of SPC, specifically with a percentage
of 0.15%.
Finally, it can be concluded that the use of a solid polycarboxyl-
ate superplasticizer will allow cement producers to commercialize
cement that incorporates a high percentage of fly ash with a high
water demand. Otherwise, these types of fly ashes will be rejected
(due to the difficulty entailed in achieving a fixed workability). This
new cement will present good workability and compressive
strength.’’
Acknowledgments
The financial support of this work by the Galicia government
(PGIDIT05TMT009E) is gratefully acknowledged. In addition, the
authors wish to express their gratitude to CIMPOR Group and SIKA,
S.A. for providing the materials used in the experimental program.
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