Construction and Building Materials 48 (2013) 417–423

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Construction and Building Materials

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

Viscosity and water demand of limestone- and fly ash-blended cement

pastes in the presence of superplasticisers
O. Burgos-Montes, M.M. Alonso, F. Puertas ⇑
Eduardo Torroja Institute for Construction Science (IETcc-CSIC), Madrid, Spain

h i g h l i g h t s

 Krieger–Dougherty equation could predict the viscosity of blended cement suspensions.

 The use of mineral additions reduced the effectiveness of cement superplasticizers.
 Cement with limestone under 30% had little effect on paste rheology.
 Fly ash lowers the minimum water demand for suitable fluidity.

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

Article history: The rheological behaviour of fresh cement has a direct effect on the microstructural development of mor-
Received 19 March 2013 tar and concrete. Inasmuch as the presence of mineral additions impact cement paste rheology and con-
Received in revised form 18 June 2013 sequently its permanent microstructure and strength, a full understanding of blended cement behaviour
Accepted 9 July 2013
should be pursued. The present study addresses the joint effect of mineral additions (limestone and fly
Available online 7 August 2013
ash) and superplasticisers admixtures on the viscosity and water demand of cement pastes.
Cement pastes were prepared with 10, 30 or 50 wt% limestone or fly ash as mineral admixtures. Mel-
Keywords:
amine-, naphthalene- and polycarboxylate-based superplasticisers were used. Paste rheology was stud-
Viscosity
w/c Ratio
ied in terms of variations in yield stress and viscosity with the solids content and amount of mineral
Cement pastes additions added. The strength and microstructure of the blended cement pastes were determined at vis-
Limestone cosity values of 1.5 Pas. in the presence of superplasticisers.
Fly ash The findings showed that the Krieger–Dougherty equation could be used to determine the effect of sol-
Rheology ids content on the apparent viscosity of limestone- and fly ash-blended cement suspensions, as well as
Superplasticisers the effect of superplasticisers. Adding less than 30% limestone to cement had no effect on paste rheology:
i.e., the w/c ratios for minimum and optimal workability were similar to the ratios for ordinary cement.
However, adding fly ash did lower the minimum water demand, and the optimal amount of water needed
for suitable fluidity. The inclusion of 10% of either addition raised paste strength, while higher propor-
tions 30 or 50%) had the opposite effect. The use of mineral additions reduced the effectiveness of cement
superplasticisers.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction different factors affecting the rheological behaviour of the cement.

One of the key factors in the development of concrete micro-
structure is its fresh state fluidity. Workability is the term tradi-
tionally used to define a concrete that can be readily mixed,
shipped and placed. Workability is typically determined by means
of the slump test, although different concrete mixes with similar
slump values have been reported to behave differently during
on-site casting. Given the essential role in concrete fluidity played
by fresh cement rheology, a detailed study is needed to define the
⇑ Corresponding author.
E-mail address: puertasf@ietcc.csic.es (F. Puertas).
The physical parameters of cement pastes, which govern their
characteristics and physical behaviour under different conditions
can be studied on the grounds of their rheology [1–3].
In on-site concrete casting, the general trend is to use binders
with a high solids content but low yield stress and viscosity. This
combination ensures high performing concretes with no detriment
to their workability. Since viscosity and yield stress are generally
agreed to be exponentially related to the water/cement ratio, the
conditions for obtaining an ideal compromise between solids con-
tent and paste fluidity need to be determined [4]. That objective
can be attained by controlling both the physical–chemical charac-
teristics of cement pastes and the inter-particulate forces with the
addition of superplasticisers to the mix [5–9].

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.07.008
418 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423

Mineral additions are used in cement for economic and environ- Table 1
mental reasons, as well as to enhance mortar or concrete strength Chemical composition (%,weight) and Blaine fineness of the cement and additions
used.
and durability. Mineral additions reduce the amount of clinker
needed in Portland cement manufacture. In other words, their % p. CEM I 52.5R L FA
presence lowers the high temperature (and energy consumption) L.O.I. 2.35 43.56 6.76
required and also mitigates other adverse impacts of cement man- SiO2 20.51 0.34 46.32
ufacture. The economic and environmental advantages of the use Al2O3 5.37 0.04 31.01
Fe2O3 2.10 0.11 4.50
of this type of cements have fuelled their use the world over. Of MnO 0.02 0.01 0.05
the 27 types of common cements listed in European standard MgO 3.86 0.93 1.29
EN197-1, 26 contain some manner of mineral addition (such as CaO 57.05 54.56 4.90
limestone, fly ash, blast furnace slag, silica fume or burnt shale). Na2O 0.64 0.36 0.34
K2O 1.44 – 1.34
The mineral additions chosen for the present study were limestone
TiO2 0.16 0.01 1.53
and fly ash, both listed in European standard EN197-1. Their effect P2O5 0.13 0.08 0.98
on paste rheology constituted the object of the research conducted. SO3 6.37 – 0.98
Limestone-blended cements have been widely studied. Their Sireact – 0 36.4
durability and mechanical strength are similar to the values found Blaine (m2/Kg) 501.7 – –

in the non-blended cements, and compressive strength remains ESBET (m2/g) 1.22 4.38 2.70
high at replacement ratios of up to 25% [10–16]. Another mineral Dv(lm) 10 1.19 0.81 1.80
50 7.08 3.58 13.81
addition used in cement compositions is pozzolanic aluminosili-
90 22.46 35.14 59.33
ceous fly ash, whose presence in cement has beneficial effects, such
as higher late-age mechanical strength. It also affords improved
concrete durability by constraining the expansion associated with
Table 2
the reaction between the aggregate and the alkalis in cement [17– Density values of CEM I 52.5R and blended cements.
20]. Since the use of these mineral additions may also alter paste
rheology [5,7,8], further studies are needed to through more light CEM

on the subject. I 52.5R 10L 30L 50L 10FA 30FA 50FA

The use of mineral additions has been generally thought to im- Density(g/cm3) 3.15 3.05 2.97 2.93 3.00 2.78 2.60
prove end product performance, although it has negative effect on
the workability [21,22]. The main reason given for such behaviour
Table 3
is that the large specific surface of these fine powders generates a
Physical and chemical characteristics of the admixtures used.
high water demand. This effect is observed primarily when silica
fume is the mineral addition used. It is not always present, how- Admixture PNS PMS PCE
ever, when other mineral additions are chosen. The literature has Solid content (%) 39.6 41.9 40.9
reported that some mineral additions lower water demand and Mw (Da) 136,995 78,828 59,596
Mn 25,695 7315 35,923
raise slump [2,4,11,23,24]. Improved workability and lower water
Rotational viscosity (mPas) 51.11 31.50 118.20
demand in fly ash-blended cements is attributed to the fact that %C 43.78 18.65 51.67
its spherical particles can readily roll over other particles, reducing %S 9.13 10.65 0.30
inter-particulate friction and raising paste fluidity [4,22,25,26]. In %H 4.53 3.98 8.14
limestone-blended cements, however, no consensus has been %N 0.80 22.17 0.17
Na (ppm) 31,400 55,280 2820
reached on the effect of the addition on paste fluidity. Some
K (ppm) 340 0.2 10
authors have observed improvements in rheological properties, pH 8.5 8 4.5
especially yield stress, plastic viscosity and water demand
[8,23,27], while others have found cement rheology to be adversely
affected by limestone [21,28].
Three commercial superplasticisers admixtures were also added: a naphtha-
A number of authors [5,8,21,29] studying the effect of super- lene-based (PNS), a melamine-based (PMS) and a polycarboxylate-based (PCE)
plasticisers admixtures on cement paste rheology, have reported product. Their physical-chemical characteristics are given in Table 3.
that the adsorption of part of the admixture onto the mineral addi-
tions in blended cements alters their behaviour and ultimately
their effect. 2.2. Methodology
In other words, the rheological behaviour of fresh cement di-
2.2.1. Paste rheology
rectly affects the microstructure development and strength behav- Cement paste rheological behaviour was determined with a Haake Rheowin Pro
iour of mortars and concrete. In light of the foregoing, the present RV1 rotational viscometer fitted with a grooved Z38S (Haake) cylindrical rotor to
study focuses on the joint effect of mineral additions (limestone or avoid slippage. Behaviour was studied with different solids contents. The solids
fly ash) and superplasticisers on cement paste viscosity and water content in a cement paste, defined as its volume fraction ð/Þ, is related to the
water/cement (w/c) ratio as shown in following equation:
demand and the concomitant impact on microstructure and
strength.
/ ¼ ðqw =qc Þðw=c þ ðqw =qc ÞÞ ð1Þ
2. Materials and methodology
where qw and qc are water and cement density, respectively.
2.1. Materials The cement pastes were prepared by mixing 100 g of cement and the amount of
water established for each trial with a mechanical blade stirrer for 3 min. Six milli-
The study was conducted with CEM I 52.5 R commercial Portland cement (here- gram of PNS and PMS polymers/g cement and 2 mg of PCE polymer/g of cement
after CEM I) and limestone (L) and fly ash (FA) mineral additions. The chemical com- were added to the mixing water (the optimal dosages were determined in an earlier
position and specific surface of the materials are listed in Table 1. Six blended study) [5].
cements were prepared in the laboratory with CEM I and 10, 30 or 50 wt% limestone In the rheological tests, the cement pastes were subjected to pre-shear at 100 s-1
or fly ash and respectively labelled CEM 10L, CEM 30L, CEM 50L, CEM 10FA, CEM for 1 min, return to a rotor velocity of 0 s-1, re-ramping to 100 s-1 in 12 min and
30FA and CEM 50FA. Each cement was blended in a mixer for 2 h. Table 2 lists lastly a gradual reduction in speed to 0 s-1 in a further 12 min. The downward shear
the densities of the cements used. rate values were fit to the Bingham equation (Eq. (2)), in which the y-intercept
 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423
determines the yield stress (s0) and the slope of the regression line the plastic vis-
cosity of the paste (g). In all cases the rheological curves exhibited the same behav-
iour and the downward arm of the shear rate curves fit the Bingham equation:
:
s ¼ s0 þ gðcÞ ð2Þ
2.2.2. Paste strength and microstructure
Prismatic specimens measuring 1  1  6 cm were prepared with CEM I and
blended cements, CEM 10L, CEM 30L, CEM 50L, CEM 10FA, CEM 30FA and CEM
50FA with the w/c ratio found in rheological trials for viscosity 1.5, as described
in Section 3.1 below and shown in Fig. 3.
The pastes were mixed as described in European standard EN-196-1 in an Iber-
test 32-040E mixer. Each mould was filled with two lifts of cement and dropped
60 times on the flow table after each lift was cast. The specimens were chamber-
cured at 22 °C and 99% relative humidity for 24 h and subsequently removed from
the moulds and stored in a humidity chamber until the test time (2, 7 or 28 days).
Compressive strength was determined at the test ages on an Ibertest Autotest
200/10 hydraulic test frame as specified in Spanish and European standard
UNE-EN 196-1.
Unblended CEM I 52.5R paste strength, found under the same conditions as the
strength for the experimental materials, was adopted as the control. In other words,
the strength for blended pastes with no superplasticiser was compared to the CEM I
52.5R paste strength with no superplasticiser, while the strength for the pastes pre-
pared with PNS or PCE was compared to the strength observed for CEM I 52.5R
pastes with the same superplasticiser.
One 28-day specimen of each type of cement was immersed in acetone to stop
the cement hydration reactions and subsequently vacuum-dried. Total porosity and
pore size distribution of cement pastes were determined by means of a Micromer-
itics Autopore IV 9500 analyser. Additionally the morphology of the 28-day CEM
50L and CEM 50FA pastes was studied under a Hitachi S-4800 Scanning Electron
Microscope (SEM/EDX).
3. Results and discussion
3.1. Paste rheology
Cement paste behaviour is determined by physical–chemical
inter-particle and particle–medium interaction. The tendency of
cement particles to agglomerate and form floccule detracts from
their flowability. The degree of agglomeration depends on the nat-
ure, composition and size of the cement particles, as well as the
water content in the medium.
Fig. 1 shows the variations in plastic viscosity (determined in
the rheological tests) with the solids volume fraction for the CEM
I 52.5R pastes, in the presence and absence of superplasticisers.
In Portland cements, viscosity (g) is related to the solids content
expressed as volume ð/Þ according to the Krieger–Dougherty equa-
tion [30]:
 ½g/m
g /
¼ 1 ð3Þ
gc /m
where gc is viscosity in the continuous phase, /m is the maxi-
mum solids content by volume and [g] is intrinsic viscosity. The
Krieger–Dougherty equation describes the effect of solids content
on cement suspension viscosity (g). The maximum solids content
depends on particle shape and particle size distribution. The maxi-
mum solids content can be calculated empirically by measuring
the viscosity of pastes with different solids contents [31] and then
fitting the results to calculate the theoretical curve.
Due to the very diverse size distribution and shape of the parti-
cles in the cements used in the present study, however, the exper-
imental data proved to fit the Krieger–Dougherty equation very
poorly. When fitted mathematically, they exhibited an exponential
curve in all cases. Nonetheless, for CEM I that exponential pattern
was observed to concur with the Krieger–Dougherty equation
predictions.
The exponential nature of the curve was an indication that ce-
ment pastes with over a given maximum solids content were not
fluid. With the addition of superplasticisers which, as expected,
raised the maximum solids content value, pastes could be prepared
419
2.5
2.0
Viscosity (Pa·s)
1.5
1.0
0.5
0.0
0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60
Solids volume fraction
Fig. 1. Apparent viscosity versus solids volume fraction for CEM I 52.5R pastes in
absence and presence of admixtures.
with lower w/c ratios. For each cement, the maximum solids value
is known as the maximum solids content ð/max Þ. Of the admixtures
used, PCE lowered water demand most effectively, while only min-
or differences in performance were found between PMS and PNS.
The variation in paste viscosity with the solids content (/) was
determined for the limestone- and fly ash-blended pastes in much
the same way as for the reference cement. The respective maxi-
mum / values were obtained by extrapolation from the maximum
viscosity values on the exponential curves obtained for cements
used. Entering this value in Eq. (1) yielded the w/c ratio required
to ensure the maximum viscosity in each paste.
The minimum w/c ratio found for the pastes (i.e., the minimum
amount of water that must be added for the pastes to flow with
maximum viscosity), with and without superplasticiser, is plotted
against the amount of mineral addition in Fig. 2.
As Fig. 2 shows the water demand was lower in the pastes pre-
pared with superplasticisers than in the reference samples. For up
to 30% limestone admixtures, the variations in the w/c ratio were
fairly insignificant, in both the absence and the presence of super-
plasticisers. When the limestone replacement ratio reaches 50%,
however, the minimum w/c ratio declined substantially (Fig. 2
above)The reduction in water demand in the 50 L limestone-
blended cement pastes containing superplasticisers was 31% for
PNS and PMS and 33% for PCE, compared to a 26% decline in the
paste with no superplasticiser. The beneficial effect of limestone
on the w/c ratio was attributed to the size and dispersion of its par-
ticles (Table 1), able to occupy small voids between cement parti-
cles [11].
When up to 30% fly ash (10FA and 30FA) was added to the ce-
ment (Fig. 2 below), the minimum w/c ratios declined slightly in
the pastes containing PSN and PMS. The pastes prepared with
PCE, by contrast, exhibited a significant drop in water demand with
30% fly ash. The addition of up to 30% fly ash was more effective
than limestone in lowering water demand. This may be due pri-
marily to the spherical morphology of the ash articles, which
would reduce inter-particulate friction and therefore raise paste
fluidity [21]. Blends with 50% fly ash also lowered the water de-
mand and improved the fluidity of the cement pastes. The decline
without superplasticisers was 40%, compared to 37% with PNS and
PMS and 39% with PCE. Here, the superplasticisers proved to be
less effective when the paste contained 50% fly ash [8]. The general
performance pattern of the superplasticisers in fly ash-blended ce-
ment was similar to the pattern observed for the limestone blends,
however, with PCE providing for the steepest decline and PNS and
PMS exhibiting identical effectiveness. Under minimum w/c
420 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423

0.50 0,50

0.45 0,45
water/cement ratio

water/cement ratio
0.40 0,40

0.35 0,35

0.30 0,30

0.25 0,25

0.20 0,20

0.15 0,15
0 10 20 30 40 50 0 10 20 30 40 50
Limestone (%) Limestone (%)

0.50 0.50
Without admixture Without admixture
PNS PNS
0.45 PMS 0.45 PMS
PCE PCE
water/cement ratio

water/cement ratio
0.40 0.40

0.35 0.35

0.30 0.30

0.25 0.25

0.20 0.20

0.15 0.15
0 10 20 30 40 50 0 10 20 30 40 50

Fly ash (%) Fly ash (%)

Fig. 3. Minimum w/c ratio determined for each paste at a viscosity value of 1.5 Pa s.
Fig. 2. Minimum w/c ratio determined for each paste at maximum viscosity value.

conditions, the scant availability of water may favour floc forma-
tion in the pastes, yielding scarcely workable materials. Further
to the present findings, the viscosity value established for suitable
workability was 1.5 Pas. The w/c ratios found for each paste (with
and without mineral additions and superplasticisers) are shown in
Fig. 3.
As the figure shows, the variation in paste w/c ratio at 1.5 Pas
was similar to that found for their maximum viscosity (see
Fig. 2). With 50% limestone and PNS and PMS, water demand
was 15% lower than in the pastes with no superplasticiser, while
with PCE the difference was 24%. Water content also declined
when fly ash was added, by 16%, 20% and 21% with PNS, PMS
and PCE, respectively. Under 1.5 Pas viscosity conditions, which
were less demanding than maximum viscosity, the difference be-
tween the effects of limestone and fly ash was smaller. When vis-
cosity was 1.5 Pas the w/c ratios were higher and solids content
consequently lower. As a result, the stabilising effect of the fly
ash particles was not as effective as at higher solids content values.
Therefore, the presence of the mineral additions studied affects
cement paste rheology, in particular water demand. The inclusion
of less than 30% limestone did not alter substantially the paste w/c
ratio. In pastes prepared with 50% limestone, however, water de-
mand declined substantially. The presence of up to 30% fly ash re-
duced the water demand slightly. As for limestone, when the fly
ash content was 50%, the w/c ratio declined substantially. When
the proportion of mineral addition was high, at 50%, the w/c ratio
dropped to nearly half. In all the cements studied, the effect of PNS
and PMS superplasticizers barely differed, while PCE was the
superplasticiser that most effectively reduced mixing water
demand.
3.2. Paste strength and microstructure
One of the determining factors in paste, mortar and concrete
microstructural development is the water/cement ratio used in
their preparation. Microstructure, in turn, determines the perma-
nent strength and durability of these materials. As the above rhe-
ological tests showed, the presence of mineral additions and
different types of superplasticisers altered the minimum w/c ratio
for a given viscosity. The effect of the minimum water/cement ra-
tios on the variations in cement paste strength and paste micro-
structural development in the presence and absence of
superplasticisers are discussed in this section. Because of the sim-
ilarity of PNS and PMS performance, only PCE and PNS were used in
these tests.
The 2-, 7- and 28-day compressive strength of limestone- and
fly ash-blended cement pastes with no superplasticiser admixture,
with PNS and with PCE were determined for given w/c ratios and a
constant viscosity value of 1.5 Pas. The strength activity index
(SAI) was found with Eq. (4) below to determine the effect of the
mineral additions on paste strength:
Blended cement strengh
SAI ¼ ð4Þ
Reference cement strength
A coefficient greater than one therefore means that the mineral
addition raised cement strength, while values of less than one de-
note lower strength in the blended cement than in the control.
The SAI values for each age studied are plotted against the pro-
portion of limestone addition in Fig. 4.
At all ages, the pastes prepared with 10% limestone and no
superplasticiser exhibited higher strength than the unblended
 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423 421

1.5 25 Microporous (< 0.01 µm)

Without admixture
2 days PNS
Mesoporous (0.05 - 0.01 µm)
1.4
Macroporous (10 - 0.05 µm)
PCE

No
1.3 Air Porous (> 10 µm)
20
1.2

No
No

No

PCE
PNS
1.1

% Cumulative

PCE
S.A.I.

PNS
15

PCE
PNS

PCE

PNS
1.0
0.9
0.8 10

0.7
0.6 5
0.5
10L 30L 50L
0
CEM I 10L 30L 50L
1.5
1.4
7 days Fig. 5. Pore size distribution (in lm units) in limestone-blended pastes at 28 days
curing.
1.3
1.2
1.1
S.A.I.

1.0
0.9
0.8
0.7
0.6
0.5
10L 30L 50L

1.5
28 days
1.4

1.3

1.2

1.1
Fig. 6. SEM micrograph of 28 day-CEM 50L pastes.
S.A.I.

1.0

0.9

0.8
0.7
0.6
0.5
10L 30L 50L
Fig. 4. SAI values for limestone-blended pastes at 2, 7 and 28 days of curing.
cement. In general, the pastes with higher limestone contents and
either PCE or PNS had SAIs of less than one, an indication that here
the addition of limestone had no beneficial effect on strength, de-
spite the lower w/c ratio observed.
The Hg porosimetry findings (Fig. 5) showed a decline in total
porosity and pores with a size higher than 0.05 lm in limestone-
blended pastes, which was steeper in the presence of a superplas-
ticiser. The pore size distribution underwent no substantial change,
however, in the presence of either rising amounts of limestone or
superplasticisers. These results may be interpreted as follows:
limestone, given its particle size and texture (see Table 1), favours
workability. That, in conjunction with its capacity to adsorb
superplasticizers [5], would explain the decline in paste w/c ratios.
Since this material also acts as a filler, its presence would lower
paste porosity.
The SEM micrograph of the 28-day sample of CEM 50L repro-
duced in Fig. 6 shows that the limestone particles form an integral
part of the paste matrix, generating a very compact microstructure.
None of these developments induced a significant increase in
strength, for the ultimate effect was not associated with the forma-
tion of more cohesive products, but only with physical events (bet-
ter particle distribution and dispersion and more compact
structures).
Fly ash-blended cement strength was affected primarily by two
factors: a refinement of particle size and type (as in the case of
limestone) and the reaction induced by its pozzolanic activity.
The former effect would be reflected to a greater extent at early
ages, whereas the pozzolanic effect would appear at later ages.
The variation in SAI with the proportion of fly ash in the cements
is shown in Fig. 7. The cements with 10% fly ash and no admixture
had SAI values of over one. At early ages, 2 and 7 days, the ash-
blended cements with superplasticisers had lower strength than
the unblended cement, with the exception of CEM10CV with
PNS. The bearing strength of 28-day cements with 10% and 30%
fly ash rose as a result of the pozzolanic reactions and the forma-
tion of more reaction product (essentially C–S–H gels). This rise
was steeper in the pastes containing admixtures, which exhibited
values of nearly 1. The SAI of the paste with 50% fly ash was the
lowest at all the ages studied, for two reasons: on the one hand,
the dilution effect induced by the mineral addition and on the
422 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423

Without admixture
1,5
PNS
1,4 2 days PCE

1,3
1,2
1,1
S.A.I.

1,0
0,9
0,8
0,7
0,6
0,5
10FA 30FA 50FA

1,5
1,4 7 days Fig. 8. SEM micrograph of 28 day-CEM 50FA pastes.

1,3
1,2 Microporous (< 0.01µm)
25 Mesoporous (0.05-0.01µm)
1,1
Macroporous (10-0.05 µm)
S.A.I.

1,0 Air porous (> 10µm)

No

No
0,9 20

PNS
PCE
No
0,8

PCE
% Cumulative

No
PCE
0,7 15

PCE
PNS

PNS
0,6

PNS
0,5
10
10FA 30FA 50FA

1,5
5
28 days
1,4
1,3
0
1,2 CEM I 52.5R 10FA 30FA 50FA
1,1
Fig. 9. Pore size distribution (in lm units) in fly ash-blended pastes at 28 days
S.A.I.

1,0 curing.
0,9
0,8
less reactive phase. When fly ash was added at a rate of 50%,
0,7 strength declined because the scant amount of water available dur-
0,6 ing hydration limited the effect of the pozzolanicity of the addition.
0,5 The use of mineral additions reduced the effectiveness of cement
10FA 30FA 50FA superplasticisers.

Fig. 7. SAI values for fly ash-blended pastes at 2, 7 and 28 days of curing. 4. Conclusions

other the high proportion of unreacted fly ash, for the amount of
water in these cements was very low in comparison to the amount
of ash present, preventing the pozzolanic reaction in many of the
particles. This effect was verified by SEM: note the large number
of cenospheres in the micrograph of the 28-day CEM50CV sample
reproduced in Fig. 8.
Fig. 9 shows paste porosity for different amounts of fly ash. The
pastes containing 50% fly ash and superplasticisers had a higher
porosity than the other samples, which would explain their lower
strength. The pastes with no superplasticisers and 10% fly ash
exhibited lower porosity, while at higher proportions of mineral
addition, porosity increased. This would be explained by the large
amount of unreacted ash, whose presence would yield a micro-
structure with scant particle packing.
In conclusion, adding 10% limestone or fly ash improved cement
strength considerably. Strength declined in cements with 30% and
50% limestone because the smaller proportion of cement generated
The main conclusions drawn from the results of this study are
listed below:
(a) Krieger–Dougherty equation could be used to determine the
effect of solids content on the apparent viscosity of lime-
stone- and fly ash-blended cement suspensions, as well as
the effect of superplasticisers.
(b) Adding limestone to cement at proportions of under 30% had
little effect on paste rheology. The w/c ratios for minimum
and optimal workability were similar to the ratios for ordin-
ary cement. When 50% of the cement was replaced with the
mineral addition, the water demand was lower.
(c) Adding fly ash lowered the minimum water demand and the
optimal amount of water for suitable fluidity.
(d) As expected, the use of superplasticisers lowered the water
demand in all the cements. The PCE-based superplasticiser
induced the steepest declines.
 O. Burgos-Montes et al. / Construction and Building Materials 48 (2013) 417–423
(e) Adding 10% limestone or fly ash improved cement strength
considerably. Higher proportions of mineral addition did
not improve mechanical strength.
(f) The use of mineral additions reduced the effectiveness of
cement superplasticisers.
Acknowledgements
This research was funded by the Spanish Ministry of Innovation
and Competitiveness under Project BIA2010-15516. The authors
wish to thank P. Rivilla, F. Gómez and A. Gil for their support in
some of the trials conducted.
References
[1] A.M. Neville. Properties of concrete. 4ª ed. England; 1998.
[2] P.F.G. Banfill. Rheology of fresh mortar. A review. In: 1st International
symposium of mortars technology. Florianopolis (Brasil); 2005.
[3] H.F.W. Taylor. Chemistry of cements. ed. URMO. Bilbao; 2000.
[4] Erdogan ST, Martys NS, Ferraris CF, Fowler DW. Influence of the shape and
roughness of inclusions on the rheological properties of a cementitious
suspension. Cem Concr Comp 2008;30:393–402.
[5] Burgos-Montes O, Palacios M, Rivilla P, Puertas F. Compatibility between
superplasticizer admixtures and cements with mineral additions. Constr Build
Mater 2012;31:300–9.
[6] Puertas F, Santos H, Palacios M, Martinez-Ramirez S. Polycarboxylate
superplasticiser admixtures: effect on hydratation microstructure and
rheological behaviour in cement pastes. Adv Cem Res 2005;17:77–89.
[7] Ghorab HY, Kenawi IM, Abdel All ZG. Interaction between cements with
different composition and superplasticizers. Mater Construcc
2012;62(307):359–80. doi: 10.3989/mc.2012.63610.
[8] Alonso MM, Palacios M, Puertas F. Compatibility between
polycarboxylatebased admixtures and blended-cement pastes. Cem Concr
Comp 2013;35:151–62. doi:10.1016/j.cemconcomp.2012.08.020.
[9] Palacios M, Bowen P, Kappl M, Butt HJ, Stuer M, Pecharromán C, et al.
Repulsion forces of superplasticizers on ground granulated blast furnace slag
in alkaline media, from AFM measurements to rheological properties. Mater
Construcc 2012;62(308):489–513.
[10] Livesey P. Strength characteristics of Portland-limestone cements. Constr Build
Mater 1991;3(5):147–50.
[11] Tsivilis S, Chaniotakis E, Badogiannis E, Pahoulas G, Ilias A. A study on the
parameters affecting the properties of Portland limestone cements. Cem Concr
Comp 1999;21:107–16.
[12] Tsivilis S, Chaniotakis E, Kakali G, Batis G. An analysis of the properties of
Portland limestone cements and concrete. Cem Concr Comp 2002;24(9):371–8.
423
[13] Ramezanianpour AA, Ghiasvand E, Nickseresht I, MAhdikhani M, Moodi F.
Influence of various amounts of limestone powder on performance of Portland
limestone cement concretes. Cem Concr Comp 2009;31:715–20.
[14] Vuk T, Tinta V, Gabrovsek R, Kaucic V. The effect of limestone addition, clinker
type and fineness on properties of Portand cement. Cem Concr Res
2001;31:135–9.
[15] Voglis N, KAkali G, Chaniotakis E, Tsivilis S. Portland-limestone cements their
properties and hydration compared to those of other composite cements. Cem
Concr Comp 2005;27:191–6.
[16] Pipilikaki P, Beazi-Katsioti M. The assessment of porosity and pore size
distribution of limestone Portland cement pastes. Constr Build Mater
2009;23:1966–70.
[17] Feldman RF, Cerette GG, Malhotra. Studies on mechanism of development of
physical and mechanical properties of high-volume fly ash-cement pastes.
Cem Concr Comp 1990;12:245–51.
[18] Papadakis VG. Effect of fly ash on Portland cement systems. Part I. Low-
calcium fly ash. Cem Concr Res 1999;29:1727–36.
[19] Li G, Wu X. Influence of fly ash and its mean particle size on certain
engineering properties of cement composite mortars. Cem Concr Res
2005;35:1128–34.
[20] Yilmaz B, Olgun A. Studies on cement and mortar containing low-calcium
flu ash, limestone, and dolomitic limestone. Cem Concr Comp 2008;30:
194–201.
[21] Artelt C, Garcia E. Impact of superplasticizer concentration and of ultra-fine
particles on the rheological behaviour of dense mortar suspensions. Cem Concr
Res 2008;38:633–42.
[22] Ferraris CF, Obla KH, Hill R. The influence of mineral admixtures on the
rheology of cement paste and concrete. Cem Concr Res 2001;31:245–55.
[23] Zhang X, Han J. The effect of ultra-fine admixture on the rheological property
of cement paste. Cem Concr Res 2000;30:827–30.
[24] Lange F, Mortel N, Rudert V. Dense packing of cement pastes and resulting
consequences on mortar properties. Cem Concr Res 1997;27(10):1481–8.
[25] Banfill PFG. Additivity effects in the rheology of fresh concrete containing
waterreducing admixtures. Constr Build Mater 2011;25:2955–60.
[26] Lee SH, Kim HJ, Sakai E, Daimon M. Effect of particle size distribution of fly
ash-cement system on the fluidity of cement pastes. Cem Concr Res 2003;33:
763–8.
[27] Diamantonis N, Marinos I, Katsiotis MS, Sakellariou A, Papathanasiou, Kaloidas
V, et al. Investigations about the influence of fine additives on the viscosity of
cemetn paste for self-compacting concrete. Constr Build Mater 2010;24:
1518–22.
[28] Magarotto R, Torresan I, Zeminian N. In: Influence of the molecular weight of
policarboxylate superplasticizers on the rheological properties of fresh cement
Procedding 11th ICCC. 2003; vol. 2: p. 514.
[29] Mikanovic N, Jolicoeur C. Influence of superplasticizers on the rheology and
stability of limestone and cement pastes. Cem Concr Res 2008;38:907.
[30] Krieger IM, Dougherty TJ. Trans Soc Rheol 1959;3:137–52.
[31] Vikan H. Ph.D. Department of Materials Science and Engineering, Norwegian
University of Science and Technology; 2005.