Construction and Building Materials 119 (2016) 308–318

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Construction and Building Materials

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

Cements with a high limestone content – Mechanical properties,

durability and ecological characteristics of the concrete
Sebastian Palm a, Tilo Proske b, Moien Rezvani b,⇑, Stefan Hainer c, Christoph Müller a,
Carl-Alexander Graubner b
a
VDZ gGmbH, Tannenstr. 2, 40476 Düsseldorf, Germany
b
Institut für Massivbau, Technische Universität Darmstadt, Franziska-Braun-Str. 3, 64287 Darmstadt, Germany
c
Dyckerhoff GmbH, Dyckerhoffstr. 7, 65203 Wiesbaden, Germany

h i g h l i g h t s

 Cements with limestone content up to 50 wt.-% can be used by an adopted concrete technology and reduction of w/c ratio to about 0.35.
 Limestone seems not to be totally inert component. The contribution of limestone to the compressive strength is also remarkable when higher amount of
Portland cement clinker is replaced with limestone.
 The production of concretes made of limestone-rich cements exhibited roughly 25% less CO2 emission, but needs approximately the same energy
demand.

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

Article history: This paper deals with the performance of concretes made of cements containing high levels of limestone
Received 8 October 2015 between 35 and 65 wt.-%. The Article mainly focuses on cements with 50 wt.-% limestone. Several exper-
Received in revised form 26 April 2016 iments regarding the fresh and hardened concrete properties were carried out. Chloride penetration,
Accepted 4 May 2016
freeze-thaw resistance, carbonation resistance and long-term deformation behavior were analyzed.
Available online 18 May 2016
The results show that concretes with cements containing up to 50 wt.-% limestone and a water/
cement-ratio of 0.35 may have sufficient properties for practical application if a stringent supervision
Keywords:
is ensured. Furthermore, these concretes can exhibit mechanical and durability properties comparable
CaCO3
Plastic viscosity
to concretes according to EN 206-1 and the German national application document DIN 1045-2 made
Mechanical properties of EN 197-1 cements. Besides, the results revealed that these properties depend highly on the limestone
Durability characteristics. Life cycle assessment analysis revealed that a cut-off up to 25% in global warming poten-
Global warming potential tial of concretes made with such cements is achievable in comparison with German average cement with
Energy demand the same performance.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction fuel and the electricity consumption [2]. It is visible that the reduc-
tion of the Portland cement clinker content in cement will reduce
1.1. Motivation the environmental impact of concrete.
The Portland cement clinker content in cement can be reduced
Concrete is known as the most widely used building material of by using supplementary cementitious materials (like ground gran-
our time. The major environmental impact of concrete comes from ulated blast furnace slag (GGBFS) as a latent hydraulic component
the CO2 emissions during cement production, which is altogether and fly ash according to DIN EN 197-1 as a pozzolanic component).
responsible for more than five percent of global anthropogenic In addition to the reduction of the environmental impact [3] the
CO2 release. In 2013 more than 4 billion tons of cement were pro- mechanical and durability properties can be improved.
duced and mainly used in the concrete industry [1]. The CO2 emis- Cements with GGBFS are allowed in practice for many decades,
sions are mainly related to the decalcination of the limestone, the e. g. in Germany or the Netherlands. Due to the technical, environ-
mental and the economic benefits, Portland composite cements
⇑ Corresponding author. (CEM II) were developed and increasingly used since early 1990’s
E-mail address: [email protected] (M. Rezvani). especially in Europe (see Fig. 1). In Portland composite cements

http://dx.doi.org/10.1016/j.conbuildmat.2016.05.009
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318 309

CEM I CEM II CEM III CEM IV CEM V

Percentage of cement types -

CEM I CEM II CEM III Others Total production

Total production ×106 [tonne]

100 40 100
Annual production [%]

CEMBUREAU EU27
80 32 80

60 24 60

40 16 40

20 8 20

0 0 0
1990
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012

2007

2008

2009

2010

2011

2012
Fig. 1. Annual production of different cement types in Germany (left) [4] and Europe (right) [source: CEMBUREAU data2014].

the clinker is efficiently used together with other main con- with an increased content of e.g. limestone is worth to be further
stituents like GGBFS, fly ash, silica fume and limestone to certain investigated and developed.
ratios. EN 197-1 limits the amount of main constituents besides
Portland cement clinker in CEM II cements to maximum value of
35 wt.-%. However, within the last years the production of CEM II 1.2. Concrete with Portland limestone cement
cements has reached a constant level, for example in Germany
due to the locally limited availability of GGBFS and fly ash (see Mechanical performance and durability of concrete made of
Fig. 1). Portland limestone cement with up to 20 wt.-% limestone are
As shown in Fig. 2, the total amount of produced GGBFS and fly already investigated in depth, e.g. [16–21]. Although limestone is
ash are nearly completely used by the cement and concrete indus- usually considered as an inert component (e.g. [16]), it may influ-
try in Germany. This means that an increased use of these con- ence the microstructure positively and improve the mechanical
stituents in the cement and concrete industry is not probably properties as well as the durability of concrete [16,22–25]. Voglis
possible in many countries. et al. [22] observed that presence of limestone in Portland lime-
For decades, Portland limestone cement CEM II-LL is used stone cement paste increases the early strength due to formation
widely in Europe [7] in accordance with the European cement stan- of tricalcium aluminum carbonate hydrates (3CaO
Al2O3
CaCO3

dard EN 197-1. For instance, in year 2012 near 27% of total pro- 11H2O). Stark et al. [26] reported that addition of 6 wt.-% of
duced CEM II in Europe were Portland limestone cements (see limestone influences the reaction products of C3S, C3A and C4AF
Fig. 3). The use of cements with a limestone content up to which affects the early strength of cement up to four days.
15 wt.-% is now allowed also in the US and Canada since 2013 Lothenbach et al. indicated that addition of finely ground calcite
and 2008, respectively [8,9]. In Europe, the cement type CEM II/ can accelerate the hydration slightly by providing more surfaces
B-LL can even contain limestone up to 35 wt.-%. According to EN for nucleation and hydration products [24]. A similar conclusion
197-1, the total organic carbon (TOC) of LL limestone is limited was also made by Proske et al. when using very fine limestone
to 0.2 wt.-%, and the content of clay minerals (obtained from fillers with a Blaine specific surface area of about 16,000 cm2/g
methylene blue test) in limestone must not exceed 1.2 wt.-%. The [27]. As a result of the aforementioned alterations of the
CaCO3 content of the limestone is not allowed to be lower than microstructure, a certain amount of limestone may contribute to
75 wt.-%. However, the use of such cements in concrete is the development of the compressive strength [28–31].
restricted on national levels for severe environmental exposures. The durability of concrete with Portland limestone cement with
Several efforts by many researchers worldwide have been car- up to 20 wt.-% limestone against freeze-thaw attack with and
ried out to develop cements which are not based on Portland without de-icing salts was amply evaluated by several researchers
cement clinker anymore [10–15]. Many of these solutions could [7,17,32,33]. Most of them found that concrete specimens with
have considerable environmental benefits. However, for the time Portland limestone cement (CEM II-L and LL) can exhibit more or
being either their technical suitability or their economic value less the same resistance against freeze-thaw attack in comparison
and the availability of the constituents are often not verified. with samples composed with Portland cement. Sprung and Siebel
Therefore, the efficient use of Portland cement clinker in cement [16] showed a relatively low freeze-thaw resistance of concrete
specimens with Portland limestone cement, if the limestone does
not meet the requirements of EN 197-1. Schmidt [17] found as well
9 that the influence of the limestone quality on the durability is
8 Total available Consumed 7.7 remarkable.
The carbonation resistance of concrete containing cement with
Mass ×10 6 [ tonne]

7
6.3 limestone up to 20 wt.-% was reported to be similar to those with
6 Portland cement [34,35]. Schmidt [17] reported that concretes
5 with Portland limestone cement show a slightly higher carbona-
tion depth compared to concretes with Portland cement but they
4
exhibit better resistance against carbonation in comparison with
2.9
3 2.7
concrete using GGBFS- and fly ash-cements. Barker and Matthews
2 [36] concluded that irrespective for concrete with Portland lime-
1
stone cement, the carbonation resistance is directly related to the
compressive strength. Such behavior was also reported by Hainer
0 [29] and Dhir et al. [37] for cements with up to 50 wt.-% limestone.
Fly ash GGBFS
In similar studies, it was observed that considering the same
Fig. 2. Annual production and consumption of fly ash and GGBFS in Germany [5,6]. compressive strength, slightly lower resistance was observed for
310 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318

Fig. 3. CEM II types in Europe in 2012 [source: CEMBUREAU data2014].

concrete samples made of Portland limestone cement in compar- packing density is advantageous. This allows the reduction of the
ison to those with Portland cement [27,37]. Studies showed that water demand and therefore simultaneously the minimization of
the chloride ion permeability of concretes made of Portland the Portland cement clinker content in the cement [27,46,47].
limestone cements is highly dependent on their w/c-ratios A sufficient workability of the concrete must be provided. Neto
[18,37,38]. Increase of limestone content up to 45 wt.-% worsens and Campiteli [48] observed that the addition of limestone up to
the chloride ion diffusion resistance for w/c-ratios between 0.45 15 wt.-% increases the viscosity but reduces the flow yield stress.
and 0.65 [38]. Tsivilis [39] concluded that the Portland limestone The reduction of the w/c-ratio and the total water (which is neces-
cement with 20 wt.-% limestone can exhibit a competitive resis- sary for concretes with very high limestone content) is limited by
tance against permeability of chloride ion compared to samples the requirements on the rheological properties. If the water con-
with Portland cement. tent is reduced, the plastic viscosity of the concrete will generally
The influence of limestone content up to 20 wt.-% and higher on increase. Proske et al. [49] concluded that the modification in par-
the long-term deformation is discussed in [37,38]. In some studies, ticle size distribution of both cement and concrete can reduce the
different conclusions were drawn for creep and shrinkage. Espion plastic viscosity to an acceptable extent, even for concretes with
[40] observed that shrinkage of ternary cements with limestone low water and high limestone powder content.
content up to 30 wt.-% is similar to that of CEM I and could be pre-
cisely predicted by available prediction models. In contrast to the 1.4. Aim and procedure of the study
shrinkage, he reported that the creep coefficient of such cements
is higher than values of CEM I and the predicted values are mostly The aim of the present study is to develop and analyze Portland
underestimated. Comparable creep and shrinkage values were limestone cements with high limestone content of up to 65 wt.-%
reported for concretes with high amounts of GGBFS and limestone for the production of sustainable concrete structures in both labo-
as concrete additions [41–43]. ratory and plant scales. In this article, mainly results of cements
The particle size distribution and the fineness of limestone play with 50 wt.-% limestone are shown. To evaluate the performance
a key role in the fresh and hardened concrete properties. Parts of of these concretes, the fresh and hardened properties were com-
the limestone should be ground finer than clinker to serve as pared to those of reference concretes. To achieve sufficient
nucleation sites and therefore enhance the progress of hydration strength and durability, the w/c—ratio had to be adjusted. Exten-
[44]. Other parts of the limestone should be ground coarser than sive experiments were conducted to answer questions regarding
clinker to provide a broader particle size distribution and therefore the fresh and hardened concrete properties as well as long-term
a better packing density and a lower water demand. characteristics of concretes made of such limestonerich cements.
These works show that concretes made of cements with high
limestone contents (up to 50 wt.-% or higher) under conventional 2. Experimental program
concrete technology conditions (e.g. low packing density and high
w/c-ratios >0.45) cannot fulfil the requirements to be used in prac- 2.1. Starting materials

tical purposes, especially due to durability issues. Modifications of For the experimental studies, cements CEM I 52.5 R, CEM I 42.5 N and CEM II/A-
conventional concrete technology are essential when the applica- LL 32.5 R from the same cement plant were chosen as reference cements. The inves-
tion of concretes made of cements with high limestone contents tigated limestone-rich cements were produced by mixing CEM I 52.5 R and differ-
(up to 50 wt.-%) is aimed. ent limestones. The clinker and the limestone were ground separately and mixed
together in the cement plant or the laboratory. Chemical and some physical prop-
erties of used cement and limestones are presented in Table 1. Limestones LL2-1
1.3. Principles for low-water concretes and LL2-2 are from the same source but were ground with different intensities to
achieve various finenesses. The particle size distribution, measured with a Cilas
laser granulometer in ethanol, of used reference cements and limestones are pre-
As was mentioned above, the performance of concrete made of sented in Fig. 4. The specific surfaces acc. to Blaine correspond with the particle size
Portland limestone cement with a limestone content above 20– distributions, while specific surfaces acc. to BET are an indicator for the clay content
35 wt.-% and common water/cementratios is reported to be critical of the limestones.
[45]. A desirable durability of the concrete cannot be achieved
unless the water/cement-ratio is reduced. Principles for the devel- 2.2. Mix proportions

opment of such concrete with reduced clinker and water content Experiments were carried out on concrete samples with different w/c-ratios
are described in [27]. This procedure suggests the use of high per- and different amounts of the Portland cement clinker component. The CEM I was
formance superplasticizer. Furthermore, the optimization of the replaced stepwise from 100 to 35 wt.-% with limestone. Four different w/c-ratios
 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318 311

Table 1
Some chemical and physical properties of reference cements and limestones.

Properties Unit CEM I 52.5 R CEM I 42.5 N CEM II/A-LL 32.5 R LL1 LL2-1 LL2-2
SiO2 [wt.-%] 21.3 20.7 17.6 0.44 17.90 17.81
Al2O3 [wt.-%] 4.21 4.15 3.48 0.18 2.81 2.80
TiO2 [wt.-%] 0.22 0.24 0.17 0.01 0.15 0.15
P4O10 [wt.-%] 0.12 0.12 0.12 0.05 0.11 0.10
Fe2O3 [wt.-%] 2.67 2.70 2.32 0.12 1.10 1.11
Mn2O3 [wt.-%] 0.07 0.07 0.07 0.04 0.03 0.03
MgO [wt.-%] 0.96 0.95 0.77 0.41 0.45 0.47
CaO [wt.-%] 64.6 64.1 63.2 54.1 42.18 41.65
SO3 [wt.-%] 3.69 3.22 2.88 0.02 0.25 0.26
K2O [wt.-%] 0.57 0.57 0.46 0.01 0.57 0.58
Na2O [wt.-%] 0.19 0.18 0.15 0.00 0.08 0.12
Na-equivalent [wt.-%] 0.57 0.55 0.45 0.01 0.46 0.50
Loss on ignition [wt.-%] 0.76 2.63 8.53 43.8 33.93 34.58
Total organic carbon [wt.-%] – – – 0.02 0.14 0.12
Methylene blue value [wt.-%] – – – 0.03 0.77a 0.33
CaCO3 content [wt.-%] – – 18.0 97.8 74.13 74.53
Blaine specific surface area [cm2/g] 5508 3032 3654 4200 10500 2700
Density [g/cm3] 3.16 3.13 3.04 2.71 2.69 2.67
BET specific surface area [m2/g] – – – 0.84 6.21 6.14
RRSB slope, n [ ] 0.9 0.8 0.8 0.8 0.7 0.6
RRSB position parameter, d́ [lm] 9.04 24.4 19.1 20 10 40
a
Measured with Blaine value of 8000 cm2/g.

CEM I 52,5 R CEM I 42,5 N CEM II/A-LL 32,5 R Table 2

Concrete series based on the cement content and w/c-ratio.
Limestone LL1 Limestone LL2-1 Limestone LL2-2
10 Unit Concrete Concrete Concrete Concrete
Passing percentage [Vol.-%]

C1 C2 C3 C4

8 Cement content [kg/m3] 280 320 335 380

w/c-ratio [ ] 0.60 0.50 0.45 0.35
Paste volume [l/m3] 290 ± 5 290 ± 5 290 ± 5 290 ± 5
6
including fine
sand fraction
4 <125 lm

2
Mercury intrusion porosimetry was conducted on small samples by means of
Pascal 140/440 apparatuses. The samples were extracted from middle part of con-
0
crete cylinders and the coarse aggregates (>2 mm) were removed. They were dried
0.1 1 10 100 1000
in oven at 105 °C up to the constant weight. Pore diameters between about 0.005–
Particle diameter [µm] 200 lm were considered in calculation of total porosity.
The accelerated chloride ion migration test was done according to [51] on C2,
Fig. 4. Particle size distribution of reference cements and limestone powders. C3 and C4 concretes at the ages of 35 and 98 days. Disc specimens /
100 mm  50 mm were prepared. A 0.2 N KOH and a 0.2 N KOH + 10% NaCl solution
were used as Anolyte and Catholyte solutions.
CIF test was used to examine the freeze-thaw resistance of the reference con-
of 0.60, 0.50, 0.45 and 0.35 were used for concrete mixtures to identify the neces- cretes and concrete made of cements with high limestone contents according to
sary w/c-ratio to achieve a comparable performance with reference concretes with [52]. Scaling and relative dynamic modulus of elasticity were measured up to 56
w/c = 0.60 or 0.50. The water content imbedded in superplasticizer was considered freeze-thaw-cycles. Since, the target concrete with cement containing 50 wt.-%
in calculation of w/c-ratios of mixtures. Depending on the w/c-ratio and the cement limestone and a w/c = 0.35 shall fulfil at least the requirement of exposure class
content, the concrete mixtures were divided into four series C1, C2, C3 and C4. More of XF1 (without de-icing salt), the application of air-entraining agent according to
details regarding the mix composition are presented in Table 2. German standard EN 206-1/DIN 1045-2 is not necessary.
The paste volume of all concrete mixtures (including fine quartz sand) was lim- Shrinkage as well as creep of the mixtures with reference cements and with
ited to 290 ± 5 l/m3. A grading curve of A/AB16 according to DIN 1045-2 was used limestone-rich cements were evaluated according to DAfStb booklet 422 [53]. Mea-
for all mixtures. Except for the concrete with w/c = 0.60, a polycarboxylatether surements were conducted on two / 150 mm  300 mm cylinders (for each mix-
(PCE) superplasticizer was added for a target consistency class F4 (490 6 flow table ture) in discrete time intervals up to 120 days or longer after casting manually by
diameter 6 550 mm). The specimens were de-molded after 24 h and stored in means of an extensometer with an accuracy of 0.001 mm. After de-molding, the
water for 6 days and in a climate chamber at (20 ± 2) °C and relative humidity of specimens were stored in water for 6 days. Top and bottom surface of shrinkage
(65 ± 5)% for 21 days prior to the tests. specimens were sealed into induce a unidirectional drying. The cylindrical com-
pressive strength was determined on three cylindrical samples for each mixture.
The load corresponding to one-third of cylindrical compressive strength was con-
sidered as the creep load. Two Ø 150 mm  300 mm specimens for each mixture
2.3. Test methods
were sawed, polished and afterward placed and loaded in steel frames under
hydraulic jacks. The temperature and relative humidity were set to (20 ± 1) °C
Flow diameter of concrete was measured according to DIN EN 12350-5. To eval-
and (65 ± 3)%, respectively, and were kept constant up to the end of test period.
uate the viscosity of mixtures, the relative rheological parameter was determined
by means of Schleibinger BT2 concrete rheometer [49] by using linear Bingham
model. All measurements were conducted 18 ± 2 min after water addition in a con-
trolled laboratory condition at 20 °C and repeated for two times. Air content of fresh 3. Results and discussion
mixtures was examined using pressure method according to DIN EN 12350-7.
Compressive strength (at 7 and 28 days) and modulus of elasticity (at 28 days) 3.1. Fresh concrete properties
of concretes were measured in accordance with DIN EN 12390-3 and
DIN EN 12390-13, respectively. Concrete prisms 100  100  500 mm3 were pro-
duced for the accelerated carbonation test [50]. The accelerated carbonation The values of table flow, fresh air content, demand of superplas-
(CO2 = 2 vol.-%) was conducted at T = (20 ± 2) °C and R.H. = (65 ± 5)% for 28 days. ticizer as well as the relative plastic viscosity for concretes made of
312 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318

Table 3
Fresh properties of concrete made of reference and limestone-rich cements.

Concrete Cement Air content [%] Table flow [mm] Superplasticizer [kg/m3] Relative plastic viscosity [Nmm/(m/s)]
C1, w/c = 0.60 CEM I 52,5 R N/A 445 0.0 9.8
CEM II/A-LL 32.5 R 3.1 485 0.0 6.7
C2, w/c = 0.50 CEM II/A-LL 32.5 R 1.0 565 1.6 8.8
C4, w/c = 0.35 CEM I 52,5 R N/A 600 3.2 59.0
CEM (50% LL1) 0.9 620 2.6 49.9
CEM (50% LL2-1) 2.2 515 5.7 23.9
CEM (50% LL2-2) 3.2 550 11.9 13.2

reference and cements with 50 wt.-% limestone are summarized in least an equal or higher compressive strengths than the reference
Table 3. The mixtures with low water content, i.e. w/c = 0.35 were mixtures with w/c = 0.50.
chosen as the critical cases for plastic viscosity. It has to be men- Fig. 6 shows the compressive strength of samples made of lime-
tioned that no superplasticizer was used for reference C1 concrete stone LL1 as a function of water/clinker-ratio and limestone con-
mixtures with w/c-ratio of 0.60. tent. Included are results tested on additional concrete samples
Considering a constant limestone content of 50 wt.-%, the con- and mortar specimens (according to DIN EN 196-1) with the same
crete made of CEM (50% LL2-1) and CEM (50% LL2-2) had generally constituents but further water/clinker-ratios and limestone con-
higher superplasticizer demand but significant lower plastic vis- tents [55,56]. It is visible that for a constant water/clinker-ratio
cosity than concrete with CEM (50% LL1). The higher demand for cements with higher limestone contents have systematically a
superplasticizer of mixtures made of LL2 limestones could be higher compressive strength. On the other hand, the deviation of
attributed to the higher clay mineral content of this type of lime- points from solid line (representing the trend for pure CEM I 52,5
stone (c.f. BET specific surface area and methylene blue values in R) becomes greater when the limestone content is increased. This
Table 1) [54]. Coarser particle distribution of LL2-2 limestone and behavior can be attributed to the reduction of total water in mixes
the interaction between the type of PCE superplasticizer and the with limestone rich cements. It leads to a higher solid volume in
limestone in CEM (50% LL2-2) resulted in a significant increase of the concrete and a lower porosity respectively (see Fig. 7 in Sec-
air content. For these mixtures (with LL2-2 limestone) also the tion 3.3). Also a lower porosity in the interfacial transition zone
higher air content could reduce the plastic viscosity in comparison can be achieved. In addition the already known and above
with mixtures made of LL1 limestone. However, it was observed described chemical reactions and physical effects could contribute
that all concretes made of cements with 50 wt.-% limestone had to the compressive strength.
an acceptable workability below 50 Nmm/(m/s) which was recog-
nized as the upper viscosity limit according to [49]. 3.3. Mercury intrusion porosimetry

Although the total porosity (capillary pores and gel porosity)

3.2. Compressive strength cannot deliver much information about microstructure and trans-
port properties of concrete, it is known as a key parameter for
The results for compressive strength after 7 and 28 days are many mechanical and elastic behavior of concrete [57,58]. The val-
drawn in Fig. 5. Concrete with CEM (50% LL2-2) and w/c = 0.35 ues of total porosity of the concretes C1 to C4 versus their com-
and 0.45 exhibit a lower compressive strength compared to con- pressive strength are plotted in Fig. 7. The total porosity for
cretes with CEM (50% LL1) and CEM (50% LL2-1), respectively, corresponding mortar of concrete mixtures was calculated based
due to its higher air content (see Table 4). However, all concretes on the obtained results of extracted sample by considering the vol-
made of cements with 50 wt.-% limestone and w/c = 0.35 had at ume of coarse aggregates (>2 mm) of 51 vol.-%. It evidences that

100 6.0
7d 28 d Air content
strength, fc,cube [N/mm2]
Concrete compressive

4.8
Air content [vol.- %]

80

60 3.6

40 2.4

20 1.2

0 0.0
CEM II/A-LL 32.5 R

CEM II/A-LL 32.5 R

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL1)

CEM (50% LL1)

CEM (50% LL1)

CEM I 42.5 N

C1, C2, w/c = 0.50 C3, w/c = 0.45 C4, w/c = 0.35
w/c =
0.60

Fig. 5. Compressive strength and air content of concrete.

 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318 313

Table 4
Comparison of modulus of elasticity, shrinkage and creep values with prediction models.

Concrete Cement fc,cyl,dry[N/mm2] E-Modulus [kN/mm2] Total shrinkage strain at Creep coefficient after 84 days
112 d [mm/m] of loading [ ]
Exp. Predicted EC2a Exp. Predicted Exp. Predicted
EC2a MC10b EC2a MC10b
C1 CEM II/A-LL 32.5 R 26.3 32.01 28.67 0.24 0.39 0.34 1.61 1.75 3.32
C2 CEM II/A-LL 32.5 R 38.8 35.65 32.23 0.30 0.36 0.33 1.15 1.44 2.15
C3 CEM (50% LL1) 26.7 32.63 28.81 0.30 0.52 0.44 1.70 1.74 3.10
CEM (50% LL1) 49.1 38.97 34.58 0.27 0.46 0.39 1.20 1.15 1.56
C4 CEM (50% LL2-1) 52.1 37.44 35.20 0.38 0.46 0.39 1.80 1.09 1.46
CEM (50% LL2-2) 36.8 29.86 31.73 0.41 0.49 0.42 1.77 1.48 2.16
a
Eurocode 2.
b
Model Code 2010.

140
- Limestone LL1
Compressive strength, fc,28d,dry [N/mm2]

- Specimens 6 days in water then 21 days at 20°C/65% R.H.

120
 Mortar  Concrete CEM I 52,5 R
65/35 Plant cement
50/50 Plant cement
100 35/65 Plant cement
70/30 Lab cement
50/50 Lab cement
40/60 Lab cement
80 30/70 Lab cement
25/75 Lab cement

60
Clinker
Limestone
(CEM I 52,5 R)
fc,dry,cube150 = 273 e-2.6 (water/clinker)
40
where:
clinker = 0.95 × CEM I 52,5 R
20

0
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75
Water / Clinker [-]

Fig. 6. Contribution of limestone to compressive strength: compressive strength versus water/clinker-ratio.

12 12
CEM II/A-LL 32,5 R
CEM (35% LL1)
10
Total porosity [vol.-%]

CEM (50% LL1)

10
Total porosity [%]

CEM (50% LL2-1)

8 CEM (50% LL2-2)
CEM (65% LL1)
y = 0,7301x + 1,8206
6 8 R² = 0,8089

CEM II/A-LL 32,5 R

4
CEM (35% LL1)
CEM (50% LL1) 6
2 CEM (50% LL2-1)
CEM (50% LL2-2)
CEM (65% LL1)
0 4
20 30 40 50 60 70 80 90 100 4 6 8 10 12
Concrete compressive strength, fc,cube [N/mm²] Excessive water [vol.-%]

Fig. 7. Compressive strength versus porosity of investigated concrete samples. Fig. 8. Influence of excessive water on the total porosity of the extracted samples
(concrete without aggregates >2 mm).

the compressive strength of concretes can be directly related to the

total porosity. Furthermore, the evaporable water for each mixture 3.4. Carbonation resistance
was calculated for concrete mixtures based on the information
provided by Power and Brownyard’s [59] (excessive water = total The measured carbonation depth on selected concrete samples
water 0.27  clinker) and is plotted against the total porosity with different limestone contents of cement and w/c-ratios are
of the samples (see Fig. 8). As expected the total porosity depends presented in Fig. 9. The carbonation depth increases with increas-
mainly on the evaporable water in concrete mixture. Hence a fur- ing limestone content of the cement. Though for cement with
ther reduction of the excessive water by reducing the total added 50 wt.-% limestone a carbonation resistance similar to the refer-
water would lead to lower total porosity and consequently a higher ence concrete can be obtained if the water/cement-ratio is reduced
strength. to 0.35.
314 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318

Carbonation depth ●2 vol.-% CO 2 concentration ●20°C Temperature 16

Compressive strength ●65% Relative humidity CEM II/A-LL 32,5 R -Specimens 6 days in water
-21 days at 20°C/65% R.H.

strength, fc,cube [N/mm²]

16 100 14

Concrete compressive
Carbonation depth [mm]

CEM (35% LL1) -Then 28 Tage in 2.0 vol.% CO 2

Carbonation depth [mm]

CEM (50% LL1)
12 75 12 CEM (50% LL2-1)
CEM (50% LL2-2)
10
8 50 CEM (65% LL1) y = 29,167x -12,346
R² = 0,9394
8
4 25
6
0 0
4
CEM II/A-LL 32.5 R

CEM II/A-LL 32.5 R

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL1)

CEM (35% LL1)

CEM (50% LL1)

CEM (65% LL1)

2

0
0,30 0,40 0,50 0,60 0,70 0,80 0,90

C1, w/c C2, w/c C3, w/c C4, w/c = 0.35 Water / Clinker [-]
= 0.60 = 0.50 = 0.45
Fig. 10. Carbonation depth versus water/clinker-ratio.
Fig. 9. Carbonation depth of concretes after 28 days storage in 2 vol.-% CO2
concentration.

Chloride ion migration coefficient

70
35 days
In Fig. 10 the correlation between water/clinker-ratio and car- 60
98 days
bonation depth is shown. It is visible that the carbonation resis- 50
tance of mixtures with different limestone contents is strongly

[10-12 m²/s]
40
dependent on the water/clinker-ratio. However, it seems that the
limestone LL2-1 has a certain contribution to the carbonation resis- 30
tance. One reason could be the high finesses and the high contents 20
of alkali in the limestone LL2 which could result in a pore solution 10
which increases the carbonation resistance. 0

CEM II/A-LL 32,5 R

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL1)

CEM (50% LL1)

CEM (50% LL1)

CEM I 42,5 N

3.5. Rapid chloride migration test

Fig. 11 illustrates the chloride migration coefficient of concretes C2, w/c = 0.50 C3, w/c = 0.45 C4, w/c = 0.35
C2, C3 and C4 at ages of 35 and 98 days. It can be seen that the pen-
Fig. 11. Chloride penetration on concretes C2, C3 and C4.
etration of chloride ions is highly depending on the w/c-ratio. For
all concrete series, the concretes with CEM (50% LL2-2) exhibited
relatively higher chloride permeability due to the high air content
of these mixtures. On the other hand, concretes composed of CEM 60
Chloride ion migration coefficient

CEM I 42,5 N
(50% LL1) and CEM (50% LL2-1) with w/c = 0.35 had a migration CEM II/A-LL 32,5 R
coefficients less than 20  10 12 m2/s which are comparable with 50 CEM (50% LL1)

both reference mixtures. Fig. 12 reveals that in general, the chlo- CEM (50% LL2-1)

40 CEM (50% LL2-2)

ride ion migration of all mixtures is in a good correlation with their
[10-12 m²/s]

compressive strength. This implies that a higher total air content

leads to both a decreased compressive strength and an increased 30
chloride ion migration. However the compressive strength seems
20
to be more sensitive to air content. It has to be mentioned that
none of the concretes show optimal behavior with regard to chlo-
10
ride penetration compared to commonly used slag containing CEM Migration coefficient 35 days = 12316 fc-1.572
R² = 0.83
II or CEM III cements.
0
20 30 40 50 60 70 80 90 100
28 d compressive strength, fc,cube,dry [N/mm²]
3.6. Freeze-thaw resistance
Fig. 12. Chloride ion migration against 28-d compressive strength of concrete
samples.
The results of freeze-thaw tests on concretes containing
cements with 50 wt.-% limestone LL1 and LL2-2 are plotted (as
the dominant cases) in Figs. 13 and 14, respectively. The results
indicate that the w/c-ratio should be at least reduced to maximum 3.7. Modulus of elasticity, shrinkage and creep
value of 0.45 to reach an acceptable resistance of samples with
CEM (50% LL1) against freeze-thaw attack. Comparison between The values of modulus of elasticity are presented in Table 4.
two limestone types reveals the higher resistance of concretes with Results show that except concrete made of cement with lime-
CEM (50% LL2-2) compared to CEM (50% LL1). This was more pro- stone LL2-2, all other concrete samples had the measured modulus
nounced for internal damage. This improvement arises from higher of elasticity larger than calculated values after Eurocode 2 [60].
air content of these mixtures which was discussed earlier. How- Total shrinkage strain and values for specific creep at different
ever, concretes with different limestone types show different resis- time intervals are illustrated in Table 4 and Fig. 15. Findings show
tance against freeze-thaw attack. that the shrinkage rate of cements with 50 wt.-% limestone is
 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318 315

C2, w/c = 0.50, CEM I 42.5 N C2, w/c = 0.50, CEM II/A-LL 32.5 R The higher shrinkage of concretes with LL2 limestones is maybe
C2, w/c = 0.50, CEM (50% LL 1) C3, w/c = 0.45, CEM (50% LL 1) due to the higher BET surface area of the these limestones (denotes
C4, w/c = 0.35, CEM (50% LL 1)
the presence of clay minerals). In this case, in the presence of
1.4 120
water, the disjoining pressure (as a function of surface area and

rel. dyn. E-Modulus [%]

1.2 100 chemo-electrical properties of clay particles) is drastically
Scaling [kg/m²]

1.0 increased (initial swelling). When the internal relative humidity

80 drops due to progress of drying, the particles will later attract each
0.8
60
other more thus the higher shrinkage can be observed in clay-
0.6 contaminated limestones [61,62]. Furthermore, the higher alkali
0.4
40 content of these limestone including Na2O and K2O may also be
responsible for the higher shrinkage [63,64].
0.2 20
The creep behavior of different concretes with 50 wt.-% lime-
0.0 0 stone was somehow similar to shrinkage. All mixtures with LL2
0 14 28 42 56 0 14 28 42 56 limestones had specific creep values larger than concrete made
Freeze-thaw-cycle Freeze-thaw cycle of LL1 limestone. On the other hand, mixtures with CEM (50%
LL2-2) crept about 53% more than C2 reference mixture under
Fig. 13. Freeze-thaw resistance of concretes made of reference and CEM (50% LL1)
the same applied load, while the concrete C4 with CEM (50% LL
cements (value at 56 FTC for CEM I not available).
1) showed a similar specific creep to reference mixture C2.
The total shrinkage strains as well as creep coefficients were
C2, w/c = 0.50, CEM I 42,5 N C2, w/c = 0.50, CEM II/A-LL 32,5 R calculated for 112 days and 84 days of drying and loading, respec-
C2, w/c = 0.50, CEM (50% LL2-2) C3, w/c = 0.45, CEM (50% LL2-2) tively, according to Eurocode 2 [60] and Model Code 2010 [65].
C4, w/c = 0.35, CEM (50% LL2-2) These values are compared with the experimental values and are
1.4 120 presented in Table 4. In these calculations, the cements containing
rel. dyn. E-Modulus [%]

1.2 100 50 wt.-% of limestone were assumed as class S cements. This clas-
1.0
sification is based on the low compressive strength of such
Scaling [kg/m²]

80 cements with w/c = 0.50 (see Fig. 5).

0.8
The results show that concretes with LL1 limestone had always
60
0.6 shrinkage strain and creep coefficients values below to the pre-
0.4
40 dicted values. In contrast, concretes made of LL2 limestones had
experimental shrinkage values larger than the calculated values.
0.2 20
For the creep experiments, the Eurocode could predict the creep
0.0
0 coefficients more realistic than Model Code equations.
0 14 28 42 56 0 14 28 42 56 Moreover, both total shrinkage and creep values were calcu-
Freeze-thaw-cycle Freeze-thaw-cycle lated using another approach. In this approach the effect of lime-
stone on the class and development of compressive strength was
Fig. 14. Freeze-thaw resistance of concretes made of reference and CEM (50% LL2-
neglected and the calculation was conducted for CEM I 52,5 R
2) cements (value at 56 FTC for CEM I not available).
(class R). The values obtained for both approaches are plotted in
Figs. 16 and 17. It should be mentioned that this approach is not
highly dependent on the quality of limestone. Comparison of applied on the concretes made of CEM II/A-LL since the provision
shrinkage strains after 112 days reveals that the mixture with for this type of cement is already exist in Eurocode and Model
CEM (50% LL1) had a comparable shrinkage value to both reference Code.
concretes. While all mixtures with LL2 cements exhibited 65 and As it can be seen, both Eurocode and Model Code predict the
40% higher values for shrinkage strains in comparison with refer- total shrinkage more precisely using first approach than the second
ence concrete with CEM II/A-LL and w/c = 0.50 and 0.60, approach. However, the difference between the approaches is not
respectively. significant for the creep values.

C1, w/c = 0.60, CEM II/A-LL 32.5 R C2, w/c = 0.50, CEM II/A-LL 32.5 R

C3, w/c = 0.45, CEM (50% LL1) C4, w/c = 0.35, CEM (50% LL1)

C4, w/c = 0.35, CEM (50% LL2-1) C4, w/c = 0.35, CEM (50% LL2-2)

0.5
Specific creep [(mm/m)/(N/mm²)]

0.08
Total shrinkage [mm/m]

0.4
0.06

0.3
0.04
0.2

0.02
0.1

0.0 0.00
0 28 56 84 112 140 168 196 224 252 0 28 56 84 112 140 168 196
Age of concrete [d] Time after loading [d]

Fig. 15. Shrinkage deformation (left) and specific creep values (right) of C2, C3 and C4 concretes.
316 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318

0.8 Table 5
Total shrinkage [mm/m]

Eurocode - As cement class S

Eurocode - CEM I 52,5 R + limestone as concrete addition
Database used for LCA-analysis.
Model code - As cement class S
0.6 Model code - CEM I 52,5 R + limestone as concrete addition Material Source GWP [kg CO2-eq./kg] Total energy [MJ/kg]
Experiment
CEM I 52.5 R [66] 0.8189 3.4724
0.4 CEM I 42.5 N [66] 0.7976 3.5367
CEM II/A-LL 32.5 R [67] 0.7009 2.8264
0.2 German average cement [69] 0.6917 2.4513
Model Code
Model Code

Eurocode

(EPD)
Eurocode

Limestone [66] 0.0278 0.4440

0.0 River gravel 2/16 mm [66] 0.0023 0.0341
CEM II/A-LL 32.5 R

CEM II/A-LL 32.5 R

CEM (50% LL2-1)

CEM (50% LL2-2)

CEM (50% LL1)

CEM (50% LL1)

River sand 0/2 mm [66] 0.0023 0.0353
Quartz fine sand [66] 0.2865 4.6924
Superplasticizer [68] 0.7721 18.244

C1, w/c = 0.60 C2 ,w/c = 0.50 C3, w/c = 0.45 C4, w/c = 0.35
Ökobau.dat 2010 [66], Netzwerk Lebenszyklusdaten [67] and EFCA
Fig. 16. Comparison of experimental values with predicted values of shrinkage at [68]. In this study, the environmental aspects due to transportation
112 days of drying by using different approaches. of raw materials to the concrete plant are not included in the
database and the re-absorption of carbon dioxide was ignored.
Raw data and the results of the GWP for different concretes are
5.0 presented in Table 5 and Fig. 18, respectively. These concretes had
Eurocode - As cement class S
Creep coefficient [-]

Eurocode - CEM I 52,5 R + limestone as concrete addition compressive strengths between 55 and 80 N/mm2 and showed
4.0 Model code - As cement class S
Model code - CEM I 52,5 R + limestone as concrete addition comparable durability results. LCA indicates a significant reduction
Experiment
3.0 of GWP up to 25% by the use of cements with limestone content up
to 50 wt.-% in comparison with concrete made of German average
2.0
cement including 75% clinker, 14% GGBFS, 5% limestone and 6%
others [German average EPD]. However, according to the available
Model Code

Model Code

1.0
Eurocode
Eurocode

data set, no significant savings in total used energy was observed

0.0 compared to concretes with average cement, but a remarkable
CEM (50% LL1)

CEM (50% LL1)

CEM II/A-LL 32.5 R

CEM II/A-LL 32.5 R

CEM (50% LL2-1)

CEM (50% LL2-2)

reduction was found compared to concretes made of ordinary Port-

land cements.

5. Conclusion
C1, w/c = 0.60 C2, w/c = 0.50 C3, w/c = 0.45 C4, w/c = 0.35

Based on the experimental findings, the following conclusion

Fig. 17. Comparison of experimental values with predicted creep values at 84 days
can be drawn:
of loading by using different approaches.

1. The use of limestone-rich cements with limestone content up to

4. Life cycle assessment (LCA) analysis 50 wt.-% in structural concrete could be possible by using an
adopted concrete technology and reduction of w/cratio to about
The global warming potential (GWP) as well as total energy 0.35.
demand as the dominant environmental impacts were calculated 2. It can be concluded that the w/c-ratio is the key parameter
by using the environmental performance evaluation based on for cements with high limestone contents. The mechanical
data basis for the constituents according to GaBi database and and durability properties are extensively depending on the

- Without transport,
- Total energy demand (Primary energy (renewable and non-renewable) without energy
from secondary burning fuels)
Compressive strength [N/mm²]

300 120 2500 100

Global warming potential

Compressive strength [N/mm²]

Total energy demand [MJ]

GWP Total energy demand

(GWP) [kg CO2-eq]

Compressive strength
250 100 2000
Compressive strength
80
200 80
1500 60
150 60
185 1000 1,877 40
244 2,401 2,168 1,737
100 279 245 40
184 1,750
500 20
50 20

0 0 0 0
CEM II/A-LL 32.5 R

German EPD cement

C2, w/c = 0.50,

CEM (50% LL2-1)

CEM (50% LL1)
CEM I 42.5 N

C4, w/c = 0.35,

German EPD cement
CEM II/A-LL 32.5 R

C4, w/c = 0.35,

C2, w/c = 0.50,
CEM (50% LL2-1)
C2, w/c = 0.50,

CEM (50% LL1)

C2, w/c = 0.50,

C4, w/c = 0.35,
CEM I 42.5 N

C4, w/c = 0.35,

C2, w/c = 0.50,

C2, w/c = 0.50,

Fig. 18. LCA-analysis of selected concrete mixtures with same performance: global warming potential (left) and total energy demand (right).
 S. Palm et al. / Construction and Building Materials 119 (2016) 308–318 317

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