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Effect of fineness in clinker-calcined clays-limestone cements

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DOI: 10.1680/adcr.14.00095

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Advances in Cement Research Advances in Cement Research, 2015, 27(9), 546–556
Volume 27 Issue 9 http://dx.doi.org/10.1680/adcr.14.00095
Paper 1400095
Effect of fineness in clinker-calcined clays- Received 27/10/2014; revised 06/01/2015; accepted 09/01/2015
limestone cements Published online ahead of print 03/04/2015

Vizcaı́no Andrés, Antoni, Alujas Diaz, Martirena ICE Publishing: All rights reserved
Hernández and Scrivener

Effect of fineness in
clinker-calcined clays-limestone
cements
Leng M. Vizcaı́no Andrés José Fernando Martirena Hernández
PhD Student, Center for the Research and Development of Structures and Professor, Center for the Research and Development of Structures and
Materials (CIDem), Universidad Central de Las Villas, Santa Clara, Cuba Materials (CIDem), Universidad Central de Las Villas, Santa Clara, Cuba
Mathieu Georges Antoni Karen Louise Scrivener
PhD Student, Laboratoire de Materiaux de Construction (LMC), École Professor, Laboratoire de Materiaux de Construction (LMC), École
Polytechnique Fédéral de Lausanne, Lausanne, Switzerland Polytechnique Fédéral de Lausanne, Lausanne, Switzerland
Adrian Alujas Diaz
Postdoctoral Researcher, Faculty of Chemistry and Pharmacy, Universidad
Central de Las Villas, Santa Clara, Cuba

This paper looks at the effect of fineness of the different components in a blend containing 55% Portland cement,
30% calcined clay and 15% limestone. The calcined clay originates from a natural deposit in Cuba and contains less
than 50% kaolinite. The particle size distribution (PSD) of each of the three components was varied by using different
grinding times, and the consequences on heat release, strength development, pore structure and phase assemblage
development were investigated up to 28 d. Higher fineness of both clinker and calcined clay can considerably
improve compressive strength at all ages, while limestone fineness only plays a role at early age. The formation of
carboaluminate hydrates owing to the combined addition of calcined clays and limestone is confirmed for this case
of a mixed clay with moderate kaolinite content.

Introduction It has also been shown that blended cements with good strengths
The demand for more sustainable cements has prompted the use at early ages may be obtained by substituting clinker with a
of blended cements, where part of the Portland cement clinker is combination of kaolinitic calcined clay and limestone (Antoni et
replaced by one or more supplementary cementitious materials al., 2012; Damidot et al., 2011). For up to 45% cement substitu-
(SCM), such as fine limestone, fly ash or slag. However, there are tion by a 2:1 blend of pure metakaolin and limestone, mechanical
two major barriers to increasing the levels of substitution of 20– properties at 7 and 28 d are better than the 100% cement
30% typically seen worldwide: technical performance, especially reference. These mechanical properties could be related to the
early strength, and supply of suitable SCMs (Schneider et al., refinement of the pore structure observed by mercury intrusion
2011). porosimetry (MIP) and the formation of an important amount of
carboaluminate hydrates.
Calcined clays are being increasingly investigated, owing to
their widespread availability in the world and interesting early It was therefore decided to investigate such blends further by
reactivity as pozzolans. Metakaolin (MK), a high-purity cal- using calcined clay originating from a clay deposit with moderate
cined clay, has proven to be a highly reactive pozzolan, either kaolinitic content, identified as a potential source for an industrial
as a mineral admixture for the production of high-performance trial. The results of this industrial trial are reported elsewhere
concrete, or as a normal pozzolan in pozzolanic blends (Sabir (Vizcaı́no et al., 2015). This novel cementitious system has been
et al., 2001; Siddique and Klaus, 2009). The reactivity of MK called the limestone calcined clays cement (LC3) and is currently
is associated with the content of mineral kaolinite in the being developed in a project funded by the Swiss Development
original clays, which is known to be the most reactive clay, Agency (SDC, 2015), with the goal to introduce this blend in
after appropriate thermal treatment, in comparison with other several countries where cement demand is growing very rapidly,
clay minerals such as montmorillonite or illite (Ambroise et such as India, Thailand or Brazil.
al., 1985; Fernández et al., 2011; He et al., 2000). Recent
studies have shown that, after optimisation of calcination, This paper aims at studying the relative influence of particle size
cement substituted by 30% low-grade clay with kaolinite distribution (PSD) of each component of a ternary blend where
content below 50% can yield the same mechanical performance approximately 45% of clinker has been replaced by a 2:1 blend
as Portland cement at 28 d (Antoni, 2013; Fernández López, of calcined clay–limestone on the mechanical and microstructural
2009). properties of the resulting blended cement.

546
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

Materials Iron(III) oxide

Quartz
Description of materials and methods Kaolinite
Clinker was produced at Siguaney cement factory in Cuba.
Calcium sulfate and limestone, originated also from Siguaney,
Cuba, are used in the manufacture of plain Portland cement.
Commercial quartz fine sand K-50, supplied by Carlo Bernasconi
AG, was used as a reference to assess the individual contribution
of each clinker-replacing material; this is pure quartz.

The calcined clay originated from Pontezuela, Cuba. The com-

10 15 20 25 30 35
monly accepted activation window for kaolinite clay occurs
between 600 and 8508C (Murat and Comel, 1983; Sabir et al., Figure 2. Selected X-ray diffraction pattern from 10 to 35 (2Ł8)
2001). The clays were calcined for 60 min in a Nabertherm for raw clayey soil (on the bottom) and the same clay once
LH30/14 laboratory oven. The calcination temperature was calcined (on the top)
chosen as 7508C; this ensures complete dehydroxylation (Figure
1) and it is well below the recrystallisation temperature. The
curve of the calcined clay, presented in Figure 1, shows no quantities of quartz, feldspar and carbonates were identified.
remaining weight loss, confirming that dehydroxylation was fully Limestone used had 92% of calcium carbonate (CaCO3) as
completed. determined by thermogravimetric analysis (TGA), with minor
amounts of quartz identified by XRD.
The chemical and mineralogical composition of all materials was
characterised by X-ray fluorescence (XRF) (APC Solutions, Thermogravimetric analyses, on samples of about 50 mg pieces
Denges, Switzerland) using a Bruker AXS S4 Explorer spectro- crushed in an agate mortar, were conducted with a Mettler-Toledo
photometer operating at a power of 1 kW and equipped with a Rh TGA/SDTA 851 balance using a 10 8C/min ramp from 308C to
X-ray source. X-ray diffraction (XRD) measurements were 9008C under a 30 ml/min flow of nitrogen. The amount of
carried out on powder using a Panalytical X’Pert Pro MPD kaolinite present in the soil was estimated to be about 57% from
diffractometer in a Ł–Ł configuration using CuKÆ source the weight loss between 400 and 8008C in the TGA curve using
(º ¼ 0 .154 nm) with a fixed divergence slit size of 0 .58. Samples the tangent method, as detailed by Marsh and Day (1988). The
were scanned on a rotating stage between 48 and 658 2Ł using an TGA method probably overestimates kaolinite content because
X’Celerator detector with a step size of 0 .01678 2Ł and a time the 2:1 aluminium (Al)–clay dehydroxylation occurs at higher
per step of 30 s. XRD confirmed, besides kaolinite, the presence temperature and appears included in the tail of kaolinite dehy-
of quartz, goethite and a non-identified 2:1 clay as minor droxylation. By Rietveld refinement, the kaolinite fraction was
minerals in the calcined clay, as presented in Figure 2. Table 1 estimated to be 46%, 8% of quartz, 8% of goethite and 39% of a
gives the chemical composition of all materials tested. The 2:1 dioctahedral aluminium-clay that could not be precisely
content of gypsum in the raw material to be used to produce the identified.
cement was determined by combining XRD and XRF. Bassanite
(CaSO4.0 .6H20 was detected by XRD, with only minor traces of Clinker, limestone and calcined clay chosen for this study were
other calcium sulfates; this corresponds to around 71% bassanite separately ground in a laboratory stainless steel ball mill with
according to sulfur trioxide (SO3) content by XRF. Further, minor stainless steel grinding balls. Two grinding times, 30 and 60 min
were used, yielding a coarse and a fine material. Particle size
0·00 distributions were measured with a Malvern Mastersizer type S
laser beam granulometer, which can measure particles sizes
Raw clay
⫺5·00 ⫻ 10⫺5 Calcined clay ranging from 0 .05 ìm to 900 ìm in liquid dispersion. Ultrasonic
Derivative: 1/s

Raw kaolinite predispersion was applied for 15 min and samples were given the
⫺1·00 ⫻ 10⫺4 time to cool down to laboratory temperature prior to measure-
ment. Ground clinker and blended cements were dispersed in
⫺1·50 ⫻ 10⫺4 isopropanol, to prevent cement reaction, whereas clay minerals
were dispersed in a solution of 0 .01% poly acrylic acid (PAA)
⫺2·00 ⫻ 10⫺4 and limestone in water. A Micromeritics Accupyc 1330 V2
0 100 200 300 400 500 600 700 800 9001000
Temperature: °C
instrument was used for bulk density measurements, and a
Micromeritics Gemini 2375 V4 instrument allowed the determi-
Figure 1. Temperature derivative of the thermogravimetric nation of a specific surface (Brunauer–Emmett–Teller (BET)).
analysis of Pontezuela clay before and after calcination Samples were vacuum dried with the same apparatus at 2008C
until they reached a constant weight prior to measurement.

547
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

Oxides Calcined clay Gypsum Clinker Limestone Quartz Cement Rietveld composition

Silicon dioxide 48 .4 4 .6 18 .8 4 .1 99 .0 Tricalcium silicate 60 .3

(SiO2) (C3S)
Aluminium 29 .5 1 .4 3 .2 1 .1 ,0 .1 Dicalcium silicate 11 .1
oxide (Al2O3) (C2S)
Iron (III) oxide 16 .5 1 .4 4 .7 0 .9 0 .1 Tricalcium aluminate 3 .5
(Fe2O3) (C3A)
Calcium oxide 0 .4 36 .1 68 .0 51 .8 ,0 .1 Tetracalcium 10 .5
(CaO) aluminoferrite (C4AF)
Magnesium 1 .0 2 .3 1 .3 0 .8 ,0 .1 Calcite 6 .0
oxide (MgO)
Sulfur trioxide 1 .1 38 .6 0 .2 0 .5 ,0 .1 Quartz 0 .8
(SO3)
Sodium oxide — — 0 .5 — 0 .1 Gypsum 3 .0
(Na2O)
Potassium 0 .7 0 .4 1 .1 0 .1 0 .9 Bassanite 2 .0
oxide (K2O)
Titanium 0 .6 0 .2 0 .2 0 .1 ,0 .1 Free lime 0 .8
dioxide (TiO2)
Loss on 1 .5 14 .8 1 .5 40 .6 ,0 .1 Portlandite 2 .1
ignition

Table 1. Chemical composition by X-ray fluorescence of raw

materials and cement composition by Rietveld refinement (%)

Ternary blends were produced by blending the separately ground Table 2 gives the different combinations of materials used in the
clinker, calcined clay, limestone and gypsum in different combi- blends. The three-letter code for each blend denotes the nature of
nations of coarse and fine components, as detailed in Table 2. the clinker, calcined clay and limestone components as coarse (C)
The blends were homogenised in a Turbula1 shaker-mixer-T2F or fine (F) – for example, CFF means a blend of coarse clinker,
(Willy A Bachofen AG) for 2 h. The blend was composed of fine calcined clay and fine limestone. When a blend contains
48 .6% of clinker, 29 .0% of calcined clay, 14 .5% of limestone quartz in place of calcined clay or limestone, Q is used in place
and 7 .8% of gypsum (3 .0% sulfur trioxide). The amount of of the materials replaced.
gypsum added was chosen in order to control the reaction of the
alumina phase following the methodology of Antoni et al. (2012). The hydration of all the blends was followed by isothermal
calorimetry at 208C as cement pastes with a water-to-cement ratio
of 0 .45. No superplasticiser was used. The hydration of the pastes
Denominationa Grain fraction was stopped at 3, 7 and 28 d by solvent exchange, with
immersion in isopropanol for 7 d and drying in low vacuum
Clinker Calcined clay Limestone conditions in a desiccator for 7 d longer. The samples were
further ground to powder in a zirconia mortar with a pestle and
FFF Fine Fine Fine analysed by XRD and TGA.
FFC Fine Fine Coarse
FCF Fine Coarse Fine Mortar prisms 40 3 40 3 160 mm were made with water-to-
CFF Coarse Fine Fine cement ratio of 0 .5 according to BS EN 196-1 (BSI, 2005)
FFQ Fine Fine Quartz fine (cement here includes all the cementitious materials: clinker,
FQF Fine Quartz fine Fine calcined clays, limestone and gypsum), demoulded after 24 h and
FQQ Fine Quartz fine Quartz fine cured by immersion in tap water in a storage tank at 20  28C.
a The workability of the blends was adjusted depending on the
The first letter accounts for the clinker, the second for the calcined
clay and the third for the limestone fineness, respectively. water demand of the binder with Dynamon SX-32, a non-
sulfonated acrylic polymer superplasticiser (SP). All the inter-
Table 2. Combinations of components studied mixed mixtures needed 0 .8 wt% SP (normalised by weight of
total cement) except mix FQQ with quartz, which did not require

548
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

any superplasticiser. The compressive strengths were measured at it is a multi-component clay, containing around 90 wt% total
3, 7 and 28 d. between kaolinite, a 2:1 mixed clay and goethite; these are all
components that naturally have high surface area and only 10%
The pore structure of these samples at 28 d were characterised by quartz. It can be reasonably assumed that the quartz particles were
MIP with Porotec GmbH Pascal 140 and Pascal 440 instruments further ground during the extra grinding time, whereas the clays
up to a maximum pressure of 400 MPa. The samples were and goethite particles, already very fine, remain mostly the same
‘stopped’ and dried, by the same isopropanol exchange procedure according to the fact that the energy required to break a particle is
described above. Each measurement was repeated twice. The inversely proportional to its size.
measurements were carried out on 1 .5 g samples of paste
composed of several pieces of about 3 3 3 3 3 mm, broken using It is also noted that calcination does not bring a significant
pliers. change in the specific surface, since the BET surface of the raw
clay was 36 m2/g. This is again in accordance with previous
results, for example from Fernández et al. (2011), who have
Results
shown that full dehydroxylation of kaolinite is usually obtained
Study of particle size distribution and surfaces without significant decrease of the specific surface and no major
depending on grinding time change of PSD.
The key parameters of the PSDs measured by laser granulometry
(Dv10, Dv50 and Dv90) and specific surfaces measured by BET are Grinding the limestone brings the grain size Dv50% from 3 .42
given in Table 3. The extra grinding time decreases the Dv50 size down to 1 .05 ìm. Both coarse and fine limestone particles are
of all three components. Nominally the reduction factor for the smaller than the fine clinker grains. The grain size of the
clay is the largest (,53), then limestone (,33) and last clinker reference quartz is fine, with Dv50% of 3 .3 ìm.
(,1 .53); however, only the clinker component shows a signifi-
cant increase in the BET surface area. There are two likely The characteristics of the mixed blends were also investigated.
reasons for this. First the limestone, and certainly the clay, have a Table 4 gives the results for the FFF and the CFF blended
high tendency to form agglomerates with high internal surface combinations. There is little difference between the two; unex-
area, which may be broken up by grinding without a large change pectedly a slightly coarser distribution is observed for FFF. For
in measured particle size. Second the Dv10 of the clinker is still comparison, Table 5 presents the physical properties of the blends
rather large after 30 min grinding time at 2 .3 ìm, which is resulting from mixing, calculated by combining the PSD of each
reduced to 0 .4 after further grinding, whereas the Dv10 values for
the other two components do not change much.

In terms of the specific surface area in the blend, the calcined Combination BET: Dv10: Dv50: Dv90:
clays play a crucial role since this parameter is considerably denomination m2g1 ìm ìm ìm
higher for clay minerals related to the rest of the components, for
FFF 10 .4 0 .8 14 .6 65 .4
both grinding times. The specific surface area indeed only mar-
CFF 11 .8 0 .6 10 .3 46 .4
ginally increases with longer grinding; from 33 .3 to 35 .1 m2/g.
However, it decreases significantly the average diameter Dv50% Table 4. Measured specific surface and PSD for blends FFF and
from 10 .33 to 1 .85 ìm. Such a behaviour must be analysed in the CFF
light of the nature of this clay. As stated in the preceding section,

Material Fraction, BET: m2g1 Fraction; PSD: ìm

Fine Coarse Dv10 Dv50 Dv90 Dv10 Dv50 Dv90

Fine Coarse

Clinker 1 .4 0 .3 0 .4 7 .2 38 .8 2 .3 17 .6 61 .7
Calcined clay 35 .1 33 .3 0 .2 1 .9 10 .7 0 .7 10 .3 53 .7
Limestone 8 .5 6 .0 0 .2 1 .1 7 .1 0 .3 3 .4 25 .2
Quartz 3 .4 — 0 .6 3 .3 11 .0 — — —

Table 3. Results from BET and PSD measurements of the

different LCC components

549
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

Combination BET: Dv10: Dv50: Dv90: to completely disperse the blended cement and that the blended
denomination m2g1 ìm ìm ìm cement was significantly agglomerated. Furthermore, it seems
that the combination with the finest fraction tends to enhance the
FFF 12 .5 0 .3 3 .2 27 .4 agglomeration degree. The image of scanning electron micro-
CFF 11 .9 0 .4 6 .1 45 .2 scopy-secondary electrons mode (SEM-SE) in Figure 4 supports
this statement. To take the image, the anhydrate cement grains
Table 5. Calculated specific surface area and PSD for blends FFF were glued in a resin and observed under the SEM. The SEM
and CFF was set in ‘secondary electrons’ mode to study the morphology
of non-hydrated cement.

separated component, based on the information presented in Effect of clinker fineness

Table 3. The differences between both PSDs can be observed in Compressive strength results
Figure 3. The effect of clinker fineness on compressive strengths is shown
in Figure 5. At all ages, the strength of the finer clinker is higher
As explained above, the use of calcined clay in all blends than for the blend with the coarser clinker, the differences are
increases significantly the specific surface area of the blend, due 30% at 3 d, 14% at 7 d and 16% at 28 d.
to the high specific surface of the calcined clay, but it is not
reflected in the PSD of the corresponding real system because the
finer platy particles of calcined clays and the ground limestone
particles tend to agglomerate around the clinker particles. It can
therefore be assumed that the dispersion method combining
ultrasonic vibration and dispersion in isopropanol was not enough

4
CFF
Frequency: %

FFF
3

0
0·01 0·1 1 10 100 1000
Size: μm Figure 4. SEM-SE picture from blended cement with all
(a) components fine (FFF)
6

5
FFF
CFF
60
Frequency: %

4 55·7
Compressive strength: MPa

CFF 48·1
3 50
FFF
2 39·3
40
34·6
1
30 26·5
0 20·5
0·01 0·1 1 10 100 1000 20
Size: μm
(b)
10
3 7 28
Figure 3. Comparison of the PSD obtained experimentally by laser Curing age: d
granulometry (on the top) and by calculation combining the
different PSD of each fraction (bottom). Each letter corresponds to Figure 5. Mechanical strength of mortar prisms to assess
coarse (C) and fine (F) fraction for clinker, calcined clay and influence of clinker size at 3, 7 and 28 d. CFF: coarse clinker;
limestone, in that order FFF: fine clinker

550
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

Isothermal calorimetry 0 .4 ìm; in comparison with 2 .3 ìm for the coarser clinker. This
The isothermal calorimetry output for the pastes comparing fine early difference is responsible for most of the difference in
and coarse clinker is shown in Figure 6. The heat evolution cumulated heat, since the cumulated curves seem to be parallel
curves show that the hydration of the paste with the finer clinker after 24 h and the occurrence of the aluminate peak.
component is significantly accelerated compared to the coarse
fraction. The cumulative curves confirm the higher degree of Mercury intrusion porosimetry
hydration at 3 d. The difference in the heat of hydration is, The influence of clinker PSD on porosity at 28 d can be observed in
however, smaller than the difference in strength for the blends Figure 7, where cumulated porosity obtained by MIP is plotted as a
tested at the same age. This is most probably related to the fact function of the porosity size. With finer clinker PSD, the threshold
that percolation threshold and formation of long-range connectiv- porosity (first inflection point in the curve that is also acknow-
ity can be significantly affected by varying not only the total solid ledged as the point where the pores begin to percolate (Winslow et
volume present but also the initial size distribution and packing al., 1994)) and the total cumulated porosity are significantly
of particles, which is typically the case when using different reduced, corresponding to the higher degree of hydration.
PSDs.
Effect of fineness of calcined clays
When looking at the normalised heat evolution, it can be Compressive strength results
observed that with finer clinker the main hydration peak occurs The effect of calcined clay fineness on compressive strength is
earlier and stronger; there is an enhanced nucleation effect, given in Figure 8. At 3, 7 and 28 d, the strength is considerably
noticeable by the steeper slope of this peak. The nucleation of improved with finer calcined clay PSD in comparison with the
calcium–silicate–hydrate (C–S–H) is closely related to the surface coarser PSD. The improvement reaches 33% at 3 d and decreases
area (Costoya Fernández, 2008) and so is associated with the with curing time; nonetheless there is about 20% relative
presence of submicronic particles; the Dv10 values confirm this difference at 28 d.
point, since for the finer clinker the value is about 0 .4 ìm,
meaning that 10% of the particles have a diameter lower than In addition, the compressive strengths values of a system with
45% quartz, slightly coarser than calcined clay, are given for
140 comparison. This contributes to underline the high pozzolanicity
of the combined addition of this calcined clay from natural origin
Cumulative heat: J/g clinker

120 and limestone, improving the strength massively at all ages.

100
Isothermal calorimetry
80
Figure 9 shows the calorimetry curves of pastes made with
60 coarser and finer calcined clay. At early ages the heat evolution
curve for the fine calcined clay shows a slight increase in the
40
slope, which could again be explained by the enhancement of
FFF
20 CFF cement hydration through the creation of extra nucleation sites on
the very fine clay particles, whose average size has been de-
0
0 24 48 72 creased roughly five times through grinding.
Time: h
(a)
35
6
Heat evolution: mW/g clinker

30
Cumulated porosity: %

5
25
4 FFF
20 CFF
3
15
2 FFF
CFF 10
1
5
0
0 24 48 0
Time: h 0·001 0·01 0·1 1 10 100
(b) Porosity: μm

Figure 6. Isothermal calorimetry of pastes to evaluate the Figure 7. Mercury intrusion porosimetry results at 28 d on mortars
influence of clinker: (a) cumulated heat; (b) heat evolution. for different clinker grinding times. CFF: coarse clinker; FFF: fine
CFF: coarse clinker; FFF: fine clinker; all other being equal clinker; all other being equal

551
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

60 55·7 The calcium sulfate depletion shoulder (Jansen et al., 2012) in

FQQ the heat evolution curve occurs earlier and is narrower in the
Compressive strength: MPa

50 FCF 46·5 system with fine calcined clay than with coarser calcined clay;
FFF however, at 24 h the difference in the total heat release between
40 39·3
the two systems is small. From 24 h until 72 h, however, the
32·3 cumulated heat released by the blend with finer calcined clays is
30 29·0 higher than with coarser clay, and considerably higher than the
26·5
21·4
system with only quartz. This difference may be related to the
19·8
20 17·4 reaction of the calcined clay component and is consistent with
the increase of strength observed in mortars made with fine
10 calcined clay at 3 d in comparison with those made with coarse
3 7 28 calcined clay and the reference filler. XRD analyses have
Curing time: d
confirmed the formation of carboaluminates (see later).
Figure 8. Mechanical strength of mortar prisms to assess
influence of calcined clay. Each letter corresponds to coarse (C) Mercury intrusion porosimetry
and fine (F) fraction for clinker, calcined clay and limestone, in Figure 10 shows a comparison of the porosity and PSD between
that order; letter Q corresponds to quartz pastes made with blends of coarse and fine calcined clay. The
blend made with the fine calcined clay exhibits a considerably
higher pore refinement and a lower total porosity in comparison
with the blend made with coarse calcined clay. The pore
refinement could be caused by a combination of the effect of
improved particle packing produced by a much smaller PSD that
120
could fill up the gaps between clinker grains (Poon et al., 2001)
and the higher pozzolanic reaction of the clay seen by calorime-
Cumulative heat: J/g clinker

100 try. Finally, the threshold porosity is about ten times coarser for
the system containing 45% quartz filler and the total porosity is
80 also significantly increased, showing the link between the space
filling by the products of the pozzolanic reaction and the
60
consequent increase of the tortuosity and the improvement of the
40 compressive strength.

FQQ
20 FCF Effect of limestone fineness
FFF Compressive strength results
0 Compressive strength results at 3, 7 and 28 d for different
0 24 48 72 96
Time: hours limestone PSDs and the quartz filler for comparison are given in
(a) Figure 11. The finest limestone brings a significant increase at
6
40
Heat evolution: mW/g clinker

5
35
Cumulated porosity: %

4 30
FFF
25 FCF
3 FQQ
FQQ 20
2 FCF
FFF 15
1
10
0
0 24 48 5
Time: h 0
(b) 0·001 0·01 0·1 1 10 100
Porosity: μm
Figure 9. Isothermal calorimetry of pastes to evaluate the
influence of calcined clay: (a) cumulated heat; (b) heat evolution. Figure 10. Mercury intrusion porosimetry results at 28 d on
Each letter corresponds to coarse (C) and fine (F) fraction for mortars for different calcined clays’ grinding times. Each letter
clinker, calcined clay and limestone, in that order; letter Q corresponds to coarse (C) and fine (F) fraction for clinker, calcined
corresponds to quartz clay and limestone, in that order; letter Q corresponds to quartz

552
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

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60
55·055·7 in the slope of the heat of hydration curve at very early ages in
Compressive strength: MPa

FFQ 51·2 accordance with the literature, where it has been observed that
50 FFC fine limestone can enhance cement hydration by providing extra
FFF
40 38·3 39·3 nucleation sites for calcium–silicate–hydrates (Montanaro, 1988;
34·0 Sato and Diallo, 2010).
30 26·5
23·023·9 In limestone (for the range of particle size chosen in this study),
20 the predominant effect is nucleation until 24 h; later on, carbo-
nates react with the alumina in the system to form carboalumi-
10 nates (Matschei et al., 2007).
3 7 28
Curing time: d
Mercury intrusion porosimetry
Figure 11. Mechanical strength of mortar prisms to assess Figure 13 shows the cumulated porosity obtained by MIP as a
influence of limestone. Each letter corresponds to coarse (C) and function of the pore size for 28-d paste samples. A quartz filler
fine (F) fraction for clinker, calcined clay and limestone, in that (15%) was included as reference (FFQ) in the experiment in
order; letter Q corresponds to quartz order to assess the impact of the interaction between limestone
and calcined clay.

3 d in comparison with the coarser limestone, but the differences Limestone fineness has a relatively minor effect at 28 d, the
tend to level off with curing time and are not significant any coarser limestone giving slightly higher total cumulated porosity,
longer from 7 d onwards. The difference with the quartz filler, in accordance with the comparable compressive strengths ob-
however, is significant at all ages; the synergy obtained with tained for the corresponding systems at the same age. The total
combined addition of calcined clays with limestone brings a porosity is also reduced when using limestone.
strength enhancement of about 10–15% at all ages.
Discussion
Isothermal calorimetry results Despite the differences observed in terms of strength and
Figure 12 shows the isothermal calorimetry curves of the pastes porosity, the phase assemblages observed by differential thermo-
made with blends of coarse and fine limestone, and a reference gravimetric analysis and XRD are globally the same and, since
with inert quartz. The samples made with limestone both release the clay is too complex, it was not possible to carry out Rietveld
slightly higher heat than the sample made with quartz, which refinement to quantify precisely the variation of the phases. For
indicate some reaction, but this is small and hardly significant the sake of simplicity, the example of FFF at 3, 7 and 28 d is
because the amount of limestone reaction is low and also because given in Figure 14 and Figure 15 for differential thermogravi-
there are minor amounts of limestone in the clinker (Antoni et metric analysis and XRD, respectively). The phase assemblage
al., 2012). observed with natural clays is similar to the one observed with
pure metakaolin (Antoni et al., 2012). It is composed of
The blend made with finer limestone shows a moderate increase
35

6 30
Cumulated porosity: %
Heat evolution: mW/g clinker

25
5 FFF
20 FFC
4 FFQ
15
3
FFQ 10
2 FFC
5
FFF
1
0
0·001 0·01 0·1 1 10 100
0 Porosity: μm
0 24 48
Time: h
Figure 13. Mercury intrusion porosimetry results at 28 d on
Figure 12. Isothermal calorimetry of pastes to evaluate the mortars to assess effect of limestone particle size and differentiate
influence of calcium carbonate (top: cumulated heat; bottom: the filler effect from the effect of the chemical reactions. Each
heat evolution). Each letter corresponds to coarse (C) and fine (F) letter corresponds to coarse (C) and fine (F) fraction for clinker,
fraction for clinker, calcined clay and limestone, in that order; calcined clay and limestone, in that order; letter Q corresponds to
letter Q corresponds to quartz quartz

553
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution

Calcium–silicate– Hemi- and mono- 0

hydrate ⫹ ettringite carboaluminates Calcium hydrate Calcium carbonate FFF_3d

FFF_7d ⫺5·0 ⫻ 10⫺5

FFF_28d

⫺1·0 ⫻ 10⫺4

Derivative: 1/s
⫺1·5 ⫻ 10⫺4

⫺2·0 ⫻ 10⫺4

⫺2·5 ⫻ 10⫺4

⫺3·0 ⫻ 10⫺4
0 100 200 300 400 500 600 700 800 900

Figure 14. Derivative of the TGA of blend with all of the fine
components (FFF) at 3, 7 and 28 d

Hemi-
carboaluminate Calcium
Mono- hydrate Calcium
Ettringite carboaluminate Ettringite Ettringite Quartz Ettringite Quartz carbonate

28d

7d

3d

5 10 15 20 25 30
2θ angle: degrees

Figure 15. X-ray diffraction diffractogram obtained for blend

with all of the fine components (FFF) at 3, 7 and 28 d

554
Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

Offprint provided courtesy of www.icevirtuallibrary.com

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ettringite, carboaluminates (both hemi- and monocarboaluminate) Acknowledgements

and calcium–aluminate–silicate–hydrate (C–A–S–H) gel. Non- Special thanks are given to Ruben Snellings (LMC) and Dr
reacted limestone and quartz are also observed, but no strätlingite Adriaens (Leuven) for the mineralogy analysis. The authors
was detected. It might form at later ages since portlandite has would also like to thank the Swiss National Science Foundation
almost been entirely consumed at 28 d and absence of portlandite and the Swiss Development Agency for funding this work.
is a thermodynamic condition of strätlingite formation (Matschei
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Advances in Cement Research Effect of fineness in clinker-calcined clays-
Volume 27 Issue 9 limestone cements
Vizcaı́no Andrés, Antoni, Alujas Diaz,
Martirena Hernández and Scrivener

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