Calculation of k factor function for the carbonation process of lime-based plasters

Milena Pavlíková, Jaroslav Pokorný, and Zbyšek Pavlík

Citation: AIP Conference Proceedings 1863, 150005 (2017); doi: 10.1063/1.4992327

View online: http://dx.doi.org/10.1063/1.4992327
View Table of Contents: http://aip.scitation.org/toc/apc/1863/1
Published by the American Institute of Physics

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 Calculation of k Factor Function for the Carbonation
Process of Lime-Based Plasters
Milena Pavlíková1, a), Jaroslav Pokorný 1, b) and Zbyšek Pavlík1, c)
1
Department of Materials Engineering and Chemistry, Faculty of Civil Engineering, Czech Technical University in
Prague, Thákurova 7, 166 29 Prague, Czech Republic
a)
Corresponding author: milena.pavlikova@fsv.cvut.cz
b)
jaroslav.pokorny@fsv.cvut.cz
c)
pavlikz@fsv.cvut.cz

Abstract. The carbonation process of prepared lime plaster and lime based plaster with pozzolana active metakaolin is
performed in an accelerated test arrangement. The depth of carbonation head is determined using colorimetric method
and FTIR spectroscopy. Based on experimental data of carbonation head, time dependent k factor function is calculated
that points to the decelerated and retarded propagation of the carbonation process due to metakaolin used in plaster
composition.

INTRODUCTION
Carbonation is known as a neutralizing process, a chemical reaction between Ca(OH)2 and CO2 to form CaCO3
and H2O. Via this reaction the hardening of non-hydraulic hydrated lime takes place and the final structure is
formed. It is clear that the mechanism and the kinetics of the carbonation process depend strongly on the type of
lime and additive used, mineralogy, texture of plaster, the width of the walls, thickness of the plaster, and finally on
the concentration and time exposure of CO2. The rate of carbonation is one of the decisive factors that affect the
final strength and durability properties of lime based mortars and plasters. The carbonation reaction in plasters and
other alkaline materials is a rather complex mechanism composed of CO2 diffusion through the pore structure and its
dissolution in the capillary pore water where its reaction with calcium hydroxide occurs with the precipitation of
calcium carbonate crystals, known as hardening mechanism [1].
To better understand this reaction mechanism, intensive research has been carried out to clarify the diffusion
processes and the reaction speed. Based on gas diffusion in a porous medium, Van Balen [2] realised the very first
one-dimensional modelling of the lime mortar carbonation, taking into account the combined CO2 diffusion with
water vapour transport. This research has identified the interrelationship between CO2 diffusion and water content in
the plaster, considering the water produced from the carbonation reaction itself.
The other approach to model carbonation process represents application of analytical solution of modified
diffusion equation for the bodies of simple geometrical forms [3]. The precision of the results is dependent in this
case on the correctness of the carbonation describing parameters, i.e., CO2 diffusion coefficient, maximum increase
of density, CO2 concentration, etc.
Carbonation is a chemical reaction controlled by carbon dioxide diffusion which can be described with the
second Fick´s law (originally formulated in molar concentrations)

C  2C
D 2 , (1)
t x

International Conference of Numerical Analysis and Applied Mathematics (ICNAAM 2016)

AIP Conf. Proc. 1863, 150005-1–150005-4; doi: 10.1063/1.4992327
Published by AIP Publishing. 978-0-7354-1538-6/$30.00

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 where C is concentration of diffused matter (kg/m3), x is carbonation depth from the surface (m), t is diffusion
time (s), D is diffusion coefficient (m2/s). Based on Equation (1), carbonation depth can be expressed as

x  ek t , (2)

where e is a constant expressing the carbonation depth in t = 0 (m), in our case e = 0 m. The factor k (m/s1/2) is
necessary to be experimentally determined or predicted using mathematical models. The one of the often used is
semi empirical Schiessl´s model [4], the other one is model suggested by Bob [5], which introduces set of the
empirical parameters. Papadakis´ model that is considered to be the most comprehensive is based on the principle of
mass conservation [6]

2 D  CO2 
k 100 , (3)
CH   3  CSH 
where [CO2] is concentration of CO2 in the air (mol/m3), [CH] is concentration of Ca(OH)2 in the sample
(mol/m3), and [CSH] is concentration of hydrated calcium silicates phases (mol/m3).
Numerical models show that the carbonation reaction starts quickly on the outer surface of the lime plaster and
the CO2 diffusion controlled phase starts when the plaster has dried enough. The quick start and fast blockage is due
to the limited diffusion resistance at start and due to the barrier of diffusion resulting from the water produced by
carbonation [7]. This reaction runs in all of lime-based materials and is accompanied by pH decrease in the
carbonated areas (see Fig. 1). It is visible the diffusion of CO2 into the plaster and formation of CaCO3. Changes in
pH followed with this reaction can be detected due to colorimetric method using phenolphthalein indicator. A part of
sample which stays dark pink (pH>9) contains highly alkali portlandite. Colourless place indicates neutral calcite
which is a reaction product of lime carbonation.

FIGURE 1. The diffusion of CO2 during carbonation process illustrated with colorimetric method.

In literature several techniques have been presented to determine carbonation rate and carbonation processes in
lime based materials. Summary of all the methods used over the years made Lawrence [8] that listed following
methods to characterize the carbonation rate and degree: Phenolphthalein method (colorimetric method), X-Ray
Diffraction (XRD), thermogravimetric method (TG), gravimetric method, FTIR spectroscopy, elemental analysis,
scanning electron microscopy (SEM), optical microscopy, Raman spectroscopy, and ultra-sound velocity based
method.
In this paper, accelerated carbonation test was performed in order to investigate carbonation process of modified
lime-based plaster. For the comparison, also pure lime plaster was tested. The carbonation process was monitored
using the colorimetric method and FTIR analysis. Hardening of lime plaster was observed, the calculation of
carbonation depth was performed and influence of pozzolanic admixture on the carbonation process was determined.

EXPERIMENTAL
Within the experimental testing, new lime-metakaolin plaster (VOM) was studied. For the comparative purposes
the reference lime plaster (VO) was studied as well. The mixtures were prepared from hydrate lime CL90 produced
by limekiln Mokrá, Carmeuse Czech Republic Ltd., which consists mainly of Ca(OH)2 (92.2-96.6%). The rest are

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admixtures and impurities, nominally CO2 (0.4-1.5%), MgO (0.4-0.8%) and SO3 (0.1-0.3%). The applied silica
aggregate was a mix of three fractions 0.08/0.5; 0.5/1 and 1/2 mm in portion 1:1:1 produced by Heidelberg Cement
Group, Brněnské písky Inc., affiliate Bratčice, Czech Republic. Metakaolin MEFISTO K05, produced by ČLUZ
Inc., Nové Strašecí, Czech Republic, was used as a pozzolana active admixture. It is a highly active pozzolana
material (1 967 mg Ca(OH)2/g – amount of Ca(OH)2 fixed by 1 g of metakaolin), with average particle size in the
interval from 3 to 5 μm. The pozzolana activity was accessed using modified Chapelle test [9]. The dominant parts
of metakaolin represent amorphous SiO2 (55%) and Al2O3 (41%). The minority of compounds include Fe2O3, TiO2,
CaO, MgO, and Na2O. Each mixture prepared using laboratory mixing machine was casted into the cylindrical PVC
tubes with 7 cm diameter and 10 cm height, and then they were compacted using vibrating machine. The samples
were cured for a day at laboratory environment and then insulated by an epoxy resin at the circumference to ensure
one-dimensional CO2 transport. Samples were then exposed to CO2 environment in Nuire GT2000 chamber at
25±5 °C and 70±10 % of relative humidity. To perform accelerate carbonation test, CO2 concentration of 5% was
applied (the average CO2 concentration in the laboratory located in Prague, Czech Republic, was approx. 500 ppm,
i.e. 0.05%). To ensure personal safety during the experiment, CO2 concentration in the laboratory was monitored
with CO2 sensor ZG 106, whereas the concentration increased up to 650 ppm. The composition and basic physical
parameters of tested plasters are given in Table 1 [10].
TABLE 1. Composition and basic properties of researched plasters
w/d Lime hydrate Metakaolin Silica sand Bulk density Total open porosity
Plaster (-) (kg) (kg) 0 – 2 mm (kg) (kg/m3) (%)
VO 3.2 1.5 - 14.4 1 650 36.7
VOM 1.8 1.5 0.8 14.4 1 695 35.3

Since we had no image how long does carbonation of modified lime plaster take, the studied samples were firstly
tested after 24 hours of CO2 exposure and the depth of carbonation head was analysed. According to the obtained
results, the samples were studied after 16, 40, 66, 164, 652, and 816 hours of CO2 exposure. Each tested sample was
lengthwise cut immediately after it was taken out of the CO2 chamber, whereas the dust was removed by brush.
Freshly cut surface was sprinkled with 1% solution of phenolphthalein in ethanol. The determined depth of
carbonation head was calculated as the average value of four measurements using micrometre. It was explored that
the head of carbonation is a large area, which width and position during carbonation change [11]. From that reason,
IR spectrometry was used to determine the head of carbonation more precisely. Freshly cut surface of each plaster
was sampled in 1 mm slices and these segments were analysed using FTIR spectrometer Nicolet, Thermo Fischer
Scientific, in the modification of ATR technique with diamond crystal.

RESULTS AND DISCUSSION

The depth of carbonation head in the dependence on time of CO2 exposure was analysed using colorimetric
method and FTIR spectroscopy. The FTIR spectra are presented in Fig. 2a. The peak at 3 640 cm-1, whose intensity
decreases during the carbonation process, is assigned to the O-H stretching vibration of Ca(OH)2. It is clearly visible
the consumption of portlandite to form CaCO3. The broad peak having maximum at 1 410 cm-1, and peaks at 876
cm-1 and 712 cm-1 are connected with vibrations of C=O bond of the planar CO32- ions. In the case of VOM plaster
which contains pozzolana active metakaolin, CSH phases are presented by the stretching vibrations of Si-O bond of
the silicon tetrahedron centred between 870-1000 cm-1 and around 520 cm-1. The increase of the vibration intensity
means the CSH phase’s formation. Traditionally, phenolphthalein indicator measures the degree of carbonation at
pH of 9.0, whereas FTIR technique can determine the presence of CaCO3 from a level at which pH is 11.5 to
saturation with CaCO3 at pH 8.3 [12].
The measured values of carbonation depth were used to calculate k factor in the dependence on time according to
the Equation (2), i.e. the values of k for 0 – t time interval were accessed (see Fig. 2b). Comparing k factor functions
determined for reference lime-based plaster and lime-pozzolana plaster, the difference is quite apparent and clearly
demonstrates the decelerated carbonation due to the metakaolin used in plaster mix design. This plasters
performance we assign to the competitive hydration and carbonation reactions which took place in lime and lime-
pozzolana plasters. Similar results observed e.g. Cize [13] that stated the hydration reactions occur in the first place
and the carbonation reaction prevails afterwards. In our case, the formation of more complicated C-S-H and C-A-H
hydrates retarded partially the carbonation reaction in lime-pozzolana plaster.

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 a) b)

FIGURE 2 a) IR spectra of carbonated samples, b) development of k factor within carbonation.

CONCLUSION
In this paper, the carbonation process in lime and lime-metakaolin plasters was studied. For the experimental
assessment of the progressive carbonation head, phenolphthalein colorimetric method and FTIR spectroscopy were
used. The accelerated carbonation tests used in the presented work made possible to simulate carbonation process in
a short time of the experiment. Based on the experimental data of carbonation head, time dependent k factor function
was calculated pointing to the decelerated and retarded propagation of the carbonation process due to metakaolin
used in plaster composition.

ACKNOWLEDGMENTS
This research has been financially supported by the Czech Science Foundation, under project No 15-10591S.

REFERENCES
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