3rd AMIREG International Conference (2009): Assessing the Footprint of 11

Resource Utilization and Hazardous Waste Management, Athens, Greece

An investigation of the hydration and carbonation mechanisms of natural

hydraulic limes

Ch. Apostolaki, Th. Markopoulos, V. Perdikatsis and Z. Agioutantis

Department of Mineral Resources Engineering, Technical University of Crete, Hania, Greece

ABSTRACT lime and named it “Roman cement”. This name

was given due to the fact that Romans and
Natural Hydraulic Limes (NHL) are produced
Greeks had discovered the process of mixing
by firing of natural occurring raw materials,
limestone with “pozzolans” in order to produce
such as marly limestone, below the sintering
a material with hydraulic properties. The use of
temperature. NHL contains mainly portlandite
marly limestone replaced the need of mixing
Ca(OH)2 and larnite (Ca2SiO4). By combining
two materials together as done by Romans be-
NHL with aggregates, a binding material (i.e.
cause marly limestone in itself contains the nec-
mortar) is formed that can be used in restoration
essary mineralogical composition. In 1824 Jo-
and conservation applications on monuments
seph Aspin was credited with the discovery of
and historical buildings. Such materials have
an artificial hydraulic lime known as Portland
been used by Greeks and Romans since antiq-
cement. Although a precursor to the modern
uity.
Portland cement, Aspin’s discovery really bears
During restoration of historic buildings it is
no resemblance to what is known today as Port-
advisable to use compatible materials, both with
land cement. The main reason that Portland ce-
respect to their origin and to their physical and
ment became the major binding material in con-
mechanical properties.
struction from the end of the 19th century on,
This paper presents experimental results re-
was the standardization of its production (Calle-
garding the hydration and carbonation mecha-
baut, 2001).
nisms of NHL. The natural hydraulic lime was
Nowadays binders produced by firing of
prepared by firing marly limestone available on
marly limestone below the sintering tempera-
the Island of Crete and slaked in open air, which
ture, containing mainly portlandite Ca(OH)2 and
results the conversion of the CaO content to
larnite (Ca2SiO4) are known as Natural Hydrau-
Ca(OH)2. Experiments were conducted to de-
lic Limes. Natural Hydraulic Limes are very
termine the mineralogical phase changes in
important for the restoration and conservation of
NHL, during hydration and carbonation proc-
monuments and historical buildings. During
esses, as well as the portlandite crystallite size
these restoration projects the choice of compati-
formation during different slaking rate.
ble materials is the key so as to match, as
closely as possible, those used originally in or-
1. INTRODUCTION der to provide some continuity with the past in
respect to the physical and mechanical proper-
The properties of hydraulic lime were first rec- ties of NHL based mortars. Furthermore the
ognized with the discovery by John Smeath in knowledge of damages caused by the use of
1756, who by examining limes of different ori- Portland cement in the conservation of historical
gin found that those which gave the best results buildings, due to its properties (i.e., hardness,
as mortars contained a considerable proportion rigidity, impermeability, contamination of solu-
of clay matter (Lea, 2004). Forty years later in ble salts etc) increase the necessity of the usage
1796, James Parker patented natural hydraulic of NHL based mortars (Puertas et al., 1994;
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Collepardi, 1999; Ciliberto et al., 2008).
This paper is divided into two parts. The first
deals with the mineralogy and the process of
production of the end products used in the sec-
ond part as binders. The second part focuses on
the examination of carbonation and hydration
mechanisms occurring in these binders.
Current research deals with the carbonation
process of portlandite affected by factors such
as relative humidity (RH), temperature (T), con-
centration of CO2 and grain size (El-Turki et al.,
2009; Castellote et al., 2008). This paper exhib-
its the importance of mineralogical phase
changes in NHL, through hydration/ carbona-
tion processes as well as the significance of
portlandite crystallite size.
2. EXPERIMENTAL METHOD
2.1 Materials and preparation of binders
The raw materials used were marly limestone
from Crete, a pure fine crystalline calcitic mar-
ble and a pure synthetic larnite, fired at 900oC
for 12 hours. The pure synthetic larnite was
produced by mixing CaO and SiO2, in 2:1 mol
ratio. The calcination of limestone or marble
produces lime that is transformed by air or wet
slaking to portlandite (Ca(OH)2) and could be
characterized as Natural Lime (NL). During fir-
ing of marly limestones, larnite (Ca2SiO4) and
minor amounts of Ca(Al,Fe)2O4 are formed, as
well as lime that changes after slaking into the
form of portlandite.
Each of the produced NHL and NL (natural
lime) were divided into two parts. The first part
was slaked in open air with RH 55-60% (slow
hydration), and the second part was rapidly
slaked in water. Sampling took place in order to
identify, through mineralogical analysis, the ex-
act moment of complete transformation of lime
to portlandite so as to secure the desired minera-
logical composition before the carbonation
process starts. The above procedure is crucial,
since the content in free lime should be as low
as possible, and at the same time, reaction of
water with silicates and aluminates as well as
reaction of portlandite with atmospheric carbon
dioxide must be avoided to preserve the hydrau-
lic and setting properties (Mertens et al., 2007).
In addition, this mineralogical composition is of
great importance in this study in order to exam-
12
ine the mechanisms of carbonation and hydra-
tion processes.
2.2 Experimental procedure
A quantity of 3 g of both slow slaked and rapid
slaked NL along with 3 g of both slow slaked
and rapid slaked NHL were exposed in continu-
ous humidified airflow of 90% RH. Under the
same conditions a quantity of 3 g of both slow
slaked and rapid slaked NHL along with 3 g of
pure larnite were also exposed as pastes by add-
ing 6, 4 and 4 ml of deionized water respec-
tively. The samples were placed in PVC cylin-
ders of 2 cm in diameter and 2 cm height to en-
sure identical geometry and uni-directional car-
bonation on the exposed surface. From each of
the above mentioned specimens, four separate
samples were exposed. The analysis was per-
formed after curing of 0 (reference sample), 10,
20 and 30 days.
2.3 Analytical techniques
The mineralogical analysis was carried out by
X-ray powder diffraction analysis (XRD) on a
Bruker D8 Advance Diffractometer, using Ni-
filtered Cu Kα radiation (35 kV 35mA) and a
Bruker Lynx Eye strip silicon detector. Data
were collected from 4° to 70° 2θ with a step size
of 0.019°and a count time of 31.8 s per step.
The crystalline phases were identified using
the Diffrac plus Software (Brucker AXS) and
the PDF database. The presence of amorphous
phases in hydraulic binders cannot be excluded
a priori, (Gualtieri et al., 2006) therefore; co-
rundum powder has been added as an internal
standard. It allows quantification of the amor-
phous content. The quantitative analysis was
performed by the Rietveld method using the
TOPAS software program. This approach leads
to stable refinements and physically meaningful
information such as crystallite sizes, (Füllmann
et al., 2001) and profile shapes. They are char-
acterised in terms of the physical parameters de-
scribing the diffractometer and the diffraction
process (Cheary and Coelho, 1992).
Additionally Infrared (I.R) and thermo-
gravimetric analysis were performed.
Finally, chemical analyses by X-ray fluores-
cence were conducted with a Brucker S2 Ranger
spectrometer.
3rd AMIREG International Conference (2009): Assessing the Footprint of 13
Resource Utilization and Hazardous Waste Management, Athens, Greece

Table 1: Chemical and mineralogical analysis of the Table 3: Quantitative analysis of binders in t=0 days.
marly limestone. NHL NL larnite
Bulk composition of marly Insoluble Minerals rapid slow rapid slow C2S
limestone residue At0 Bt0 Ft0 Gt0 Et0
Oxides Minerals Minerals C2S 36.77 55.10 -- -- 100
SiO2 9.87 C3A 1.61 7.43 -- -- --
Al2O3 1.68 Amorf. 4.90 Amorf. 4.90 Periclase -- 1.27 -- -- --
Fe2O3 1.53 Calcite 80.22 -- -- CaO -- 1.89 -- -- --
CaO 49.05 Quartz 4.65 Quartz 4.65 Portland. 25.67 20.79 100 100 --
Chlo- Quartz 0.26 0.26 -- -- --
MgO 1.34 Chlorite 0.85 0.85
rite C4AF 2.04 7.83 -- -- --
K2O 0.52 Illite 7.64 Illite 7.64 C2SH 2.61 2.85 -- -- --
Kaolin- CA -- 0.52 -- -- --
L.O.I. 36.0 Kaolinite 1.73 1.73
ite Grossite 3.96 2.04 -- -- --
Total 99.99 Total 99.99 Total 19.78 Calcite 8.56 -- -- -- --
Arago-
Table 2: Chemical and mineralogical analysis of the NHL 1.74 -- -- -- --
nite
slow slaked binder.
Katoite 16.70 -- -- -- --
NHL slow slaked binder NHL after firing
Total 99.92 99.98 100 100 100
Oxides Minerals Minerals
SiO2 19.70 C2S 55.10 C2S 55.33
Al2O3 10.10 C3A 7.43 C3A 5.24 considerable amount after the almost total lime
Peri- transformation. Both the NL binders (rapid and
Fe2O3 2.68 Periclase 1.27 1.72 slow) in the t=0 days consists only of portland-
clase
CaO 61.30 CaO 1.89 CaO 29.85 ite. Synthetic larnite consists only of a pure
MgO 1.21 Portland. 20.79 Portlan 0.47 phase of larnite without any remnant from the
H2O 4.97 Quartz 0.26 Quartz 0.00 initial mixing material after firing.
C4AF 7.83 C4AF 7.41 Figures 1 to 5 present the mineralogical
C2SH 2.85 C2SH 0.00 changes of binders during the experiment under
CA 0.52 CA 0.00 continuous humidified airflow conditions de-
Gros- scribed above, after 0 (reference sample), 10, 20
Grossite 2.04 0.00 and 30 days. In particular Figures 1 and 2 pre-
site
Total 99.96 Total 99.98 Total 100.02 sent the changes for NHL slow and NHL rapid
binder respectively. The carbonation of port-
landite and the simultaneous increase of carbon-
3. RESULTS AND DISCUSSION ates are clearly observed in both cases. This be-
3.1 Mineralogy havior was expected, but the unexpected though
noticeable feature was the decrease of larnite
XRD phases as well as chemical analysis of the over time, which led to a further increase of car-
marly limestone and the end product of the bonates. The decomposition of larnite was
NHL slow slaked binder from the first part are CALCITE VATERITE ARAGONITE PORTLANDITE C2S
given in Tables 1 and 2 respectively. The NHL C4AF C3A C2SH CA Grossite CA2

slow slaked binder mineralogical analysis given Periclase Quartz CaO

60.000
in Table 2 is used as the initial NHL slow slaked
binder material for the experiment procedure in
50.000
%Concentration (Minerals)

zero curing time. The quantitative analysis of 40.000

the five different binders used in this experiment 30.000

on the first curing stage (t=0 days) is given in 20.000

Table 3. It is clearly shown in Table 3, that the 10.000

dominant silicate in the NHL slow slaked binder 0.000

is the dicalcium silicate (C2S). The aluminates 0 5 10 15 20 25 30 35

are tricalcium aluminate (C3A) and brown- BtN Days

milerate (C4AF). Portlandite is also present in a Figure 1: Mineralogical exchange of NHL slow slaked
binder over time.
3rd AMIREG International Conference (2009): Assessing the Footprint of 14
Resource Utilization and Hazardous Waste Management, Athens, Greece

CALCITE
C3A
ARAGONITE
C2SH
PORTLANDITE
Grossite CA2
C2S
Katoite
C4AF
Quartz
binder (Fig. 4) forms calcite, while the slow
70.000
slaked NL binder forms vaterite, aragonite and
60.000
calcite (Fig. 3). Furthermore, the total amount of
the carbonate mineral phases is higher com-
%Concentration (Minerals)

50.000

40.000
pared to the rapid slaked NL portlandite. The
same trend and behavior of portlandite is ob-
served also in NHL binders.
30.000

The most interesting observation of this spe-

20.000

10.000
cific experiment is shown in Figure 5; the de-
0.000
0 5 10 15 20 25 30 35 composition of larnite to carbonates. In the pure
AtN Days
larnite sample, the absence of portlandite in the
Figure 2: Mineralogical exchange of NHL rapid slaked reference sample (t=0) indicates that the de-
binder over time. composition of larnite took place according to
the following reactions:
100 Ca2SiO4 + 2H2O → 2Ca(OH)2 + SiO2amorph (1)
CALCITE VATERITE ARAGONITE PORTLANDITE

and
%Concentration (Minerals)

80

60
Ca(OH)2 + CO2 → CaCO3 + H2O (2)
40
This verifies the hypothesis that the reduction
20 of larnite is connected to the increase of port-
landite, which during the carbonation process
leads to the increase of carbonate mineral
0
0 5 10 15 20 25 30

GtN
Days
phases in the NHL binder. The decomposition
Figure 3: Mineralogical exchange of NL slow slaked of larnite offers higher amounts of amorphous
binder over time. SiO2 to the binder. The increase of amorphous
SiO2 improves the pozzolanic activity of the
100
binder during reaction with portlandite.
CALCITE VATERITE ARAGONITE PORTLANDITE In addition, Figure 6 shows TG/DTG curves
of the synthetic larnite after 30 days under con-
%Concentration (Minerals)

80
P

60
tinuous humidified airflow of 90% RH. The
presence of portlandite and calcite again proves
40
the decomposition of larnite according to previ-
20 ously mentioned chemical reactions.
Another very important result of this investi-
gation is connected with the crystallite size of
0
0 5 10 15 20 25 30
Days

FtN portlandite. It has been proved that the slaking

Figure 4: Mineralogical exchange of NL rapid slaked process (rapid or slow) in hydration of CaO of
binder over time. NHL or NL significantly influences the crystal-
known to us from our preliminary experiments. C2S Vaterite Aragonite Portlandite Calcite

This was the main reason for the inclusion of 100

synthetic larnite as well as the pure calcitic 90

%Concentration (Minerals)

80
marble, as reference materials, in this experi- 70

ment. The goal was to determine the mecha- 60

nisms of hydration and carbonation of the NHL 50

40
based binders. In order to verify the above 30

mechanisms the addition of the reference mate- 20

rials in the experiment were vital.

10

Consequently Figures 3 and 4 present the 0 5 10 15 20 25 30 35

carbonation mechanism of NL binders. The car-

Days

bonation of portlandite in a rapid slaked NL Figure 5: Decomposition of synthetic larnite to carbonates

over time.
 3rd AMIREG International Conference (2009): Assessing the Footprint of 15
Resource Utilization and Hazardous Waste Management, Athens, Greece

44.5 0.05 In Figures 9 and 10 the hydrated phases of

44 aluminates over time are shown. In particular
43.5
0
Figure 19 shows the X-ray diffractograms of the
NHL slow slaked binder in 0 and 30 days. Fig-

Derivate Weight
43 TG
Weight (mg)

-0.05

42.5
DTG
ure 10 shows the X-ray diffractograms of the
42
CaCO3 -0.1 NHL rapid slaked binder. In both slaking proc-
esses (slow and rapid) calcium aluminum oxide
`
41.5

hydrate (Ca3Al2O6·xH2O) and katoite

-0.15
41

40.5
Ca(OH)2
-0.2 ((CaO)3Al2O3(H2O)6) are formed. The differ-
0 200 400
o
Temperature ( C)
600 800 1000
ence between them is that in the slow slaking
Et3P process calcium aluminum oxide hydrate is
Figure 6: TG/DTG curves of synthetic larnite after 30 formed in a higher quantity than katoite, which
days under continuous humidified airflow of 90% RH. is present only in small quantities. The opposite
is true in the rapid slaked process where we see
higher quantities of katoite but significantly
20000
slow slaked NL
lower quantities of calcium aluminum oxide hy-
drate.
rapid slaked NL
L in ( C o u n ts )

Portlandite ( 0 0 1) 4. CONCLUSIONS
10000

The conclusions that can be drawn from these

experiments are as follows:
First and foremost is the unexpected decom-
0
position of larnite. Previous studies consistently
13 14 15 16 17 18

2-Theta - Scale
19 20 21 22 23
mention the hydration of larnite. The results
presented in this paper based on analysis of pure
Figure 7: Portlandite’s peak shape of rapid and slow
slaked NL binder.
larnite paste samples support the fact that both
decomposition and carbonation of larnite takes
lite size of portlandite (Figs. 7 & 8). Rapid hy- place instead of hydration.
dration produces well crystallized portlandite Of equal importance is the relationship be-
with a crystallite size > 1800 Å for the NL and tween the crystallite size of portlandite and the
> 700 Å for the NHL, while slow hydration (slow and rapid) slaking processes in the hydra-
forms poor crystallized portlandite with a crys- tion of CaO, as well as with the rate of the car-
tallite size < 250 Å for the NL and < 160 Å for bonation of portlandite. On one hand, it was ob-
the NHL. The full width of half maximum served that the rapid hydration produces well
(FWHM) is inversely proportional to the crys- crystallized portlandite, while slow hydration
tallite size. forms poor crystallized portlandite. On the other
It is also observed that the speed of the car- hand, the carbonation process of the poor crys-
bonation process of portlandite is a function of
crystallite size. In particular NL binder with the
smaller crystallite size of portlandite (Fig. 3) 4000
slow slaked NHL
shows an amount of carbonation; transformation
of portlandite to carbonates, of about 60%. In 3000 rapid slaked NHL
L in ( C o u n ts )

contrary in the NL binder with the larger crys- Portlandite (001)

tallite size of portlandite (Fig. 4) only 25% of 2000

portlandite was transformed to CaCO3 at the cium Aluminum Iron Hydroxide

Larnite

same curing period. The carbonation of the poor 1000

crystalline portlandite is 2.4 times faster than of

well crystalline portlandite. The speed of car- 0
16 17 18 19 20 21

bonation is inversely proportional to the crystal- 2-Theta - Scale

lite size. Figure 8: Portlandite’s peak shape of rapid and slow

slaked NHL binder.
3rd AMIREG International Conference (2009): Assessing the Footprint of 16
Resource Utilization and Hazardous Waste Management, Athens, Greece

1e4

6000
Sqrt (Counts)

5000

4000
Calcium Aluminum Oxide Hydrate NHL slow slaked 30days
3000
Katoite
2000

1000 Brownmillerite NHL slow slaked 0days

100

0
9 10 20 30 40 50

2-Theta - Scale
Figure 9: X-ray difractogram of the slow slaked NHL in 0 and 30 days.
2e4

1e4
Sqrt (Counts)

6000
5000 NHL rapid slaked 30days
4000 Katoite
3000

2000
Calcium Aluminum Oxide Hydrate NHL rapid slaked 0days
1000 Brownmillerite

100

0
9 10 20 30 40 50

2-Theta - Scale
Figure 10: X-ray diffractogram of the rapid slaked NHL in 0 and 30 days.

talline portlandite is 2.4 times faster than of well
crystalline portlandite, which means that the rate
of carbonation is inversely proportional to the
crystallite size.
Finally, the hydration of aluminates was also
observed. Calcium aluminum oxide as well as
katoite were the hydrated products of this proc-
ess.
Work is still in progress in order to collect
data with respect to the mechanical properties of
the above binders in order to combine them with
mechanisms of hydration and carbonation that
take place in the binders over time as well as
with physical parameters such as crystallite size.
ACKNOWLEDGMENTS
This research is supported by the General Secre-
tariat of Research and Technology of Greece
through the PENED 2003 program, contract
number 03ED604, co-funded by the European
Social Fund (75%) and National Resources
(25%).
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Resource Utilization and Hazardous Waste Management, Athens, Greece

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