Thirty-Second International Conference on Cement Microscopy

New Orleans, Louisiana USA

March 28 – April 1, 2010

The Committee of the International

Cement Microscopy Association

General Chairman

Dr. Larry Sutter

Michigan Technological University
Houghton, Michigan USA
llsutter@mtu.edu

Program Committee

Arturo Nisperos (Committee Chair)

Nisperos National & International Petrographic Services
Fresno, California USA
arturonisperos@sbcglobal.net

Paul Stutzman
National Institute of Standards and Technology
Washington, D.C. USA
stutz@nist.gov

Walter Pearce
St. Marys Cement
St. Marys, Ontario, Canada
wrpearce@vcsmc.com

Dr. Herbert Poellmann

University Halle-Salle
Halle (Saale), Germany
herbert.poellmann@geo.uni-halle.de
STABILIZATION OF VATERITE AND ARAGONITE IN CARBONATED GGBFS CEMENT
PASTE BY Na-MFP

O. Copuroglu and K. Sisomphon

Delft University of Technology, Faculty of CiTG, Materials & Environment, Delft, The Netherlands.

ABSTRACT

Recent studies revealed that carbonation reduces the frost salt scaling durability of ground granulated
blast-furnace slag (GGBFS) cement based materials through alteration of skin capillary porosity and
strength. This phenomenon is even more detrimental for GGBFS-rich cementitious systems. It has
been hypothesised that the metastable carbonates, -namely, vaterite and aragonite- are responsible for
the inferior durability performance of GGBFS-rich cement systems. However, the link between
metastable carbonates and the surface durability problems have not been characterised entirely. This
paper presents metastable carbonates in carbonated GGBFS paste and discusses their stabilization
with the help of sodium-monofluorophosphate solution treatment. Evidence was found that
metastable carbonates can be stabilised by the chemical treatment into amorphous apatite-like
formations which consequently renders a durable surface against frost salt scaling.

Keywords: GGBFS, carbonation, durability, microscopy, characterization.

TECHNICAL BACKGROUND

Frost salt scaling is the progressive loss of concrete skin under the combined attack of frost and de-
icing salts. The complete damage mechanism is currently unknown, however strong evidence has
been found that the phenomenon is mainly due to the cracking of an external salt-ice layer and crack
penetration into the material [1]. Therefore, the micromechanical properties of a concrete surface are
believed to be of paramount importance.

In the Netherlands, GGBFS cement dominates the market due to numerous economical and technical
reasons. GGBFS-rich concrete is known as a great performer against common durability problems.
However, its carbonation and related frost salt scaling durability have been demonstrated many times
as subpar.

It has been reported that metastable carbonates play a critical role in GGBFS-rich cement systems
against frost salt attack [2]. A number of researchers reported that a higher degree of carbonation
increases the surface scaling of such materials considerably [3-5]. Differential calorimetry study of
Stark and Ludwig revealed that this is because of the dissolution of metastable carbonates in de-icing
salt solution and low temperature [6]. Copuroglu et al. reported that the poor frost salt scaling
resistance might be mainly because of the carbonation shrinkage and coarsening of the slag cement
paste microstructure which decreases the tensile strength of the skin [7]. The authors also found that
surface treatment of carbonated slag cement mixtures by sodium-monofluorophosphate (Na-MFP)
solution renders a stable and poorly crystalline (or amorphous) phase which would improve the
surface quality [8]. It was found that Na-MFP enhances the surface scaling durability of carbonated
GGBFS cement-based materials [9] and evidence was found concerning the significance and role of
metastable carbonates in the surface resistance improvement (see Figure 1 and Figure 2).

Figure 1. Effect of Na-MFP surface treatment on the frost salt scaling durability of carbonated slag
cement concrete (w/c 0.45). Under identical environmental loading. Top image: carbonated slag
cement concrete. Bottom image: carbonated and Na-MFP treated concrete.

A significantly relevant analogy to the issue can be found in biomedical materials research. Calcium
carbonate (CaCO3)-calcium phosphate (CaP) mixtures are considered to be quite favourable in
creating stable formations for medical use. Several authors have reported the stabilization of
metastable carbonates into poorly crystalline apatite structures in biomaterials, e.g. [10]. Combes et
al. studied these mixtures and concluded that the metastable CaCO3 can react with CaP in conditions
similar to room temperature and create a formation related to poorly crystalline carbonated apatite
[11].

In this paper, stabilization of metastable carbonates in GGBFS cement systems with the help of Na-
MFP treatment is further characterized by X-ray diffractometry and microscopy, and the results are
linked to the issues related to frost salt scaling durability.
 EXPERIMENTAL STUDY

Background of the XRD study

Carbonation of GGBFS-rich cement paste produces considerable amount of metastable carbonates,

namely aragonite and vaterite, along with calcite (e.g. Figure 2a). The interaction between Na-MFP
and carbonated GGBFS cement paste was earlier studied in reference [8] and the results indicated a
decrease in metastable carbonate intensity and formation of amorphous phases (Figure 2b).
Therefore, a likely reaction between metastable carbonates and Na-MFP is further investigated
through an isolated reaction between synthesized metastable carbonates and Na-MFP.

a b

Figure 2. a) XRD diffractograms of 4 months lab carbonated GGBFS cement paste. b) same sample
after Na-MFP treatment. Diffractograms are reproduced from literature [8].

Specimen preparation for the XRD study

The synthesis was performed according to the method described by Chakrabarty and Mahapatra in
[12]. Aqueous Na2CO3 (1M, 530 g dissolved in 5 L H2O) and CaCl2 (1M, 735 g dissolved in 5 L
H2O) were preheated to 80 ºC. Both the solutions were simultaneously combined in the reactor at a
feed rate of 90 mL/min. The temperature of the mixture was maintained at 80 ºC until the completion
of the reaction. The hot slurry (precipitate) was allowed to cool to room temperature, filtered and
washed thoroughly with water. The wet cake was then dried overnight at 110 ºC and subsequently
ground to a fine powder. Then half of the powder was mixed with 10% Na-MFP solution for 5 days.
At the end of this period the mixture was filtered and washed with demineralized water and dried.
The powders were then analyzed by a Philips PW3710 diffractometer with Cu tube and Ni filter. The
2 diffraction range was from 0° to 80°.

Microscopy

The microstructural effects of the reaction between Na-MFP and metastable carbonates were studied
under electron and optical microscopes on the synthesised carbonate samples, as well as on the
GGBFS cement mortars which were borrowed from an extensive research program [13]. These
cylindrical mortar specimens were produced with a diameter of 55 mm and a height of 50 mm. The
mortar mixture had a European CEM III /B 42,5 N HSR LH cement with 67% GGBFS, W/C=0.45
and sand-to-cement ratio of 2.5. After three days of initial water curing the mortar samples were
exposed to 3% CO2 and 45% R.H. for 28 days. At the end of the carbonation period, half of the
samples were sprayed on the surface by 30% Na-MFP solution for 3 days with a daily dosage of 6
wetting-drying sessions. Thereafter, petrographic thin sections of mortar samples were produced
according to the technique described in [14].

Standard petrographic thin sections of the GGBFS cement mortars were studied with a Leica
DMRXP petrographic microscope equipped with polarization accessories. Photomicrographs of the
thin sections were acquired with a digital camera at 3504
2663-interpolated resolution and exported
as compressed JPG format images.

Synthesized carbonate powders with and without Na-MFP treatment were placed on the carbon
stickers for ESEM study. The study was carried out by a Philips XL30 environmental scanning
electron microscope (ESEM). The instrument was operated in “wet” state at up to 20kV and at 10
mm working distance, with these settings applied for Gaseous State Electron (GSE) imaging.

RESULTS AND DISCUSSION

The microstructures of synthesized metastable carbonates before and after the Na-MFP treatment are
presented in Figure 3. It should be noted that the metastable carbonates found in carbonated GGBFS
cement paste might not exist in a morphological configuration similar to the synthesised form.
Additionally, because several other components co-exist in carbonated paste (i.e. portlandite, C-S-H),
end products from the reaction between Na-MFP and metastable carbonates might differ. However,
in order to evaluate reactivity of the metastable carbonates with Na-MFP, the reactants were
exclusively isolated in an artificial reactor.

On the ESEM micrographs mainly the synthesised aragonite crystals were seen in cauliflower-like
formations, while individual vaterite crystals were not easily recognisable. Few irregularly
distributed euhedral calcite rhombi were also observed. After the 30% Na-MFP solution treatment, a
new binder was visible among the aragonite and presumably vaterite crystals, which are indicated by
white arrows in Figure 3 (right image).
Figure 3. Photomicrographs of synthesised metastable carbonates before (left a) and after (right)
10% Na-MFP solution treatment.

Figure 4. X-Ray diffractogram of synthesized carbonate minerals.

Further investigation into the characterization of this reaction was carried out by XRD. The X-ray
diffractogram of the synthesized metastable carbonates is presented in Figure 4. Aragonite, vaterite
and calcite minerals are indicated over the intensity peaks.

In Figure 5, the XRD analysis of the synthesised carbonates after 10% Na-MFP treatment is given. In
the results, there were mainly two highlights observed; a decrease in metastable carbonate intensity
and an introduction of a new amorphous phase. The decrease in carbonates intensity after 10% Na-
MFP treatment was especially noticed for vaterite and aragonite phases while calcite intensity
seemed to be stable after the treatment. The most significant intensity drop was observed at 2-Theta
25° (vaterite), 27° (vaterite+aragonite), 33° (vaterite+aragonite) and 44° (vaterite), which gives a
good indication that there might be consumption of metastable carbonates. The second main
observation was the occurrence of the humps in the X-Ray diffractogram between approximately
26°- 35° and 40°- 50° which generally indicates an amorphous structure.

The results out of the XRD study was further supported with optical microscopy photomicrographs.
In Figure 6 comparisons between carbonated and carbonated/Na-MFP treated GGBFS cement
mortars are presented. The images were captured in four different filter configurations, namely cross-
polarized light (XPL), plane-polarized light (PPL), cross-polarized light with lambda plate and
fluorescent light. Most significant results were the slight densification of the carbonated cement
matrix and strong amorphization of the Na-MFP treated zone. The transformation of highly
birefringent carbonate-rich matrix into amorphous structure upon Na-MFP treatment can be clearly
seen in Figure 6c and Figure 6d.

Figure 5. X-Ray diffractogram of synthesized carbonate minerals after 10% Na-MFP treatment.

The amorphous solid produced by the reaction between Na-MFP and carbonate phases is believed to
be an amorphous analogue of apatite (Ca5(PO4)3(F,Cl,OH)). The increase in surface scaling
durability after the Na-MFP treatment is not only due to reduction of capillary porosity but also due
to a reasonably high hardness of the amorphous apatite which increases the overall hardness and
tensile strength of the concrete surface. This in turn improves the frost salt scaling resistance which is
directly related to the mechanical properties of the concrete surface. In Figure 7, the condition of the
mortar surface after the Na-MFP treatment is presented on stitched thin section photomicrographs. In
the figures, the depth of carbonation is approximately 3mm. In this example the Na-MFP treatment
was seen to influence the top 1.5mm where this entire zone is transformed into an amorphous solid,
the capillary porosity was decreased thereby and had a significantly higher surface scaling durability.
Figure 6. Comparison of carbonated GGBFS cement mortar (left) and the same mortar after 30%
Na-MFP solution treatment (right). The images represent (from top row to bottom); PPL, XPL, XPL
with lambda plate and UV light.
 Na-MFP zone
original carbonated zone

remaining carbonated zone

uncarbonated
zone

Figure 7. Condition of carbonated GGBFS cement mortar before (left) and after (right) Na-MFP
treatment. Amorphization of the carbonated cement paste is indicated as Na-MFP zone. Image
dimensions are ~1.8
5.1mm, Cross polarized light image.
 CONCLUSIONS

In the light of the results of earlier studies, this study highlighted the following points:

1. The results show that the Na-MFP solution treatment on the microstructure of carbonated
GGBFS cement paste systems is beneficial with respect to surface durability.
2. Upon the treatment carbonated cement matrix transforms into amorphous solids, possibly
analogous to apatite. The amorphization can be clearly observed by polarized light microscopy
and supported by the XRD study.
3. Upon Na-MFP treatment, the capillary porosity of the carbonated GGBFS cement paste becomes
denser which additionally contributes to the surface micromechanial quality and frost salt scaling
resistance.

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