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"Final draft"

Characterization of Calcium Carbonate, Calcium Oxide and Calcium Hydroxide as

Starting Point to the Improvement of Lime for their Use in Construction

Miguel Galván-Ruiz1, Juan Hernández2, Leticia Baños3, Joaquín Noriega-Montes4 and Mario E.

Rodríguez-García5

1
Associated Professor. División de investigación y Posgrado, Facultad de Ingeniería,

Universidad Autónoma de Querétaro. Centro Universitario Cerro de las Campanas s/n 76010,

Querétaro, México. CETIS 105-SEP, carr. a Tlacote s/n, Querétaro, Qro. 76148. Email:

mgr@uaq.mx

1
2
Associated Professor. CETIS 105-SEP, carr. a Tlacote s/n, Querétaro, Qro. 76148 Email:

jnhdez22@gmail.com
4
Associated Researcher. Universidad Nacional Autónoma de México, Instituto de

Investigaciones en Materiales. Ciudad Universitaria, C.P. 04510, México D. F. Correo E:

simin@servidor.unam.mx
1
Associated Professor. División de Investigación y Posgrado, Facultad de Ingeniería,

Universidad Autónoma de Querétaro. Centro Universitario Cerro de las Campanas s/n 76010,

Querétaro, México. Email: joaquin@uaq.mx

Aplicada y Tecnología Avanzada, Departamento de Nanotecnología, Querétaro, A. P. 1-1010,

C.P. 76000, México. Email: marioga@fata.unam.mx

Abstract. In this paper a complete characterization of lime cycle transitions is described. CaCO3

was collected from a Mexican mine and was processed to obtain Ca(OH)2 trough CaO. When the

calcium hydroxide interacted with the CO2 in the air forming CaCO3, the lime cycle is

completed. Crystal structure and spectroscopy characterization was carried out to get knowledge

lime cycle CaCO3→CaO→Ca(OH)2→CaCO3 deeply. The changes in the crystalline structures

were described using XRD by powder to accomplish phase identification. SEM was done to

examine the morphology, topology, crystal structure and crystalline growth habit. DLS was used

to determine the particles size distribution of Ca(OH)2. FTIR was done to identify molecules and

atomic bonds. Finally, ICP-MS were done to get quantitative analyses. These results are a

contribution to the restoration and construction industry fields, as well as a starting point to new

possible applications of lime in current engineering.

2
CE Database subject headings: lime characterization, calcium carbonate, calcium oxide,

calcium hydroxide, construction.

Introduction

Lime is a burned variety of limestone (CaCO3), commonly known as quicklime (CaO) or

hydrated lime (Ca(OH)2). Initially limestone is extracted, crushed, and sieved; then it was fed

into a kiln for preheating and calcination at temperatures between 900-1200°C, decomposing it

into calcium oxide (CaO) and carbon dioxide (CO2). The original CaCO3 looses 44% of its

weight during calcination; afterward, the material is cooled and crushed. That is followed by

hydratation process during slaking with the addition of an adequate water amount to satisfy the

chemical water affinity, thereby transforming the oxide into hydroxide. During hydratation, an

exothermic reaction is produced and the solid nearly doubles its volume. As a final stage, the

carbonation process where Ca(OH)2 acquires CO2 from the environment closes the cycle,

returning to the starting point (Galván-Ruiz et al., 2009). Raw material may have pollutants, or

these could be added due to the calcination of fossil fuels and addition of water during

hydratation (Galván-Ruiz et al., 2007). Boynton (1980) remarks the importance of lime for

construction which has been extensively documented. Even though lime mortars has been used

for centuries by earlier civilizations in many of the greatest structures, the Romans were the first

to use it as a construction material, developing manufacturing methods based on natural cement

and creating appropriate construction techniques (Delatte, 2001). In the 18th century, Smeaton

started a scientific knowledge of the hydraulic limes which later derived in cement technology.

Since the 19th century, the appearance of ordinary Portland cement (OPC) produced significant

decreases in the use of lime because OPC offer fast setting and greater strength (Hill, Holmes

3
and Mather, 1992). The numerous environmental benefits to be gained to a return to more wide

range uses of lime in buildings and construction are considerable. Some of those well known

factors include: production requires lower temperatures using less energy than OPC with less

greenhouse emissions; tolerates some degree of movement in the masonry, as compared to the

stronger mortar based on OPC. The less able is it to allow the movement. The deterioration

caused by salts from the alkalis contained in OPC, however not in lime compounds. Lower

thermal conductivity, higher impermeability and better adhesion to the ordinary masonry

materials compared to OPC based products. Water retention which means that lime continues

absorbing water into their mass and holds this water in it (Holmes and Wingate, 2003).

Furthermore, mortars are dynamic materials; they continue interacting with their environment

after the hardening and carbonation processes. The structures of crystalline phases were studied

through X-ray diffraction (XRD) and scanning electron microscopy (SEM) in order to obtain

information related to the particles morphology. Complementary energy dispersive spectroscopy

(EDS) was done to ascertain a semi-quantitative elemental analysis. Dynamic light scattering

was used to determine the Ca(OH)2 particles size distribution. Atomic absorption spectroscopy

(AAS), ion chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS)

were applied to obtain a quantitative elemental analysis and FT-IR was utilized to single out the

molecules bonds. This report presents the physicochemical and mineralogical transitions

produced during the lime manufacturing process as starting point to the improvement and return

to appropriate uses of lime in the construction industry.

Experimental

Sampling

4
Three different samples were studied and labeled as follow: SA1corresponds to CaCO3, SA2 to

CaO and SA3 to Ca(OH)2. Sample SA1 was obtained by collecting three samples of

approximately 250 g from 12 different positions of limestone bank and repeatedly quartered

down mixing all parts until a representative sample was derived. Sample SA2 was obtained as

representative quick lime (CaO) from the kiln. Finally, sample SA3 was acquired from the

Ca(OH)2 warehouse. All these samples were kept in a vacuum to avoid chemical reactions.

Methods

X-ray Diffraction (XRD)

The X-ray diffraction patterns of SA1, SA2 and SA3 were done on a diffractometer (Siemens

D5000, Germany) operated at 35 kV accelerating voltage and 15 A current, using Cu Kα

re made at room temperature at a

range of 10 to 70° on 2θ with a step size of 0.05°.

Scanning Electron Microscopy (LV-SEM)

The microstructure and morphology of SA1, SA2 and SA3 samples were done using a Scanning

Electron Microscope (SEM) (Jeol JSM 5600, Japan) using secondary electrons. The microscope

was operated at 20 kV accelerating voltage.

Dynamic Light Scattering (DLS)

Particle size distribution of sample SA3 was determined using DLS (Brookhaven Instruments

BI-APD, USA) with 632.8 nm red laser, 90° scattering angle, 25°C ambient temperature and 5

µs step time. 0.02 g of Ca(OH)2 was mixed with 20 ml of distiller water and stirred by hand at

room temperature for 5 min. The first measurement was made immediately after stirring, the

5
second was done fifteen minutes later and the final one was taken 30 min after that. This was

done in order to differentiate the complete particle size distribution.

Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)

Additional quantitative elemental analysis of the three samples was obtained by mass

spectrometry (Thermo Elemental Mass system X-series ICP-MS, Standard Sample Introduction

System, USA).

Fourier Transform Infrared (FTIR)

FTIR Spectra were obtained by using spectrophotometer (Bruker vector 33, USA). Sample

preparation consisted of mixing fine powders of each sample SA1, SA2 and SA3 with KBr

powder. The specific technique used in the sample analysis was that of diffuse reflectance

spectroscopy. The commercial samples were taken as references: CaCO3 (Baker analyzed

99.9%), CaO (Fermont 96.9%) and Ca(OH)2 (Fermont 96.4%).

Results and discussion

XRD

The results of the analysis are presented in the outline of X-ray diffractograms used for phase

identification. Figure 1a shows the X-ray diffraction pattern of SA1 samples produced from a

hexagonal crystal structure corresponding to calcite (CaCO3). These peaks were identified using

card No. 5-586 from International Center for Diffraction Data (ICDD) (see letter C). Other peaks

from a hexagonal crystal structure corresponding to quartz (SiO2) (card No. 46-1045 ICDD)

were identified as Q. The rest of the peaks are weaker signals corresponding to muscovite

6
(KAl2(Si3Al)O10(OH,F)2) (card No. 07-0042 ICDD)( letter M) and kaolinite Al2Si2O5(OH)4)

(card No. 06-0221 ICDD)(letter K). The lime was obtained from a mine where quartz is a

common mineral component. Kaolinite and muscovite are also present components, but in a

lower concentration. Figure 1b shows the diffraction pattern of SA2. These pattern exhibit strong

peaks corresponding to a face centered cubic crystal structure of CaO (letter O). Other peaks

correspond to a hexagonal crystals structure from portlandite (card 44-1481 ICDD) (letter P).

The lower intensity peaks correspond to quartz and calcite. Here, quartz was collected from the

mine and it remained unchanged during calcination process because quartz fusion temperature

(2000° C) is higher than that of calcite calcination. The presence of portlandite is due to the

spontaneous reaction between CaO and moisture. Figure 1c shows the X-ray diffraction pattern

of SA3. The strong peaks correspond to a hexagonal crystal structure of portlandite (letter P). In

addition, weak peaks of calcite, quartz and monoclinic crystals of calcium silicate (card 86-0398

ICDD) (identified as CS) were also identified. Calcite in SA2 and SA3 is a remaining product

from a low-efficiency transformation process to obtain CaO and Ca(OH)2 respectively.

Figure 1

SEM

Figure 2a shows some rhombic-like blocks which have well define edges. Some ends are

fragmented and reveal a layer structure (see the inset) which illustrates the crystal growth habit

common to CaCO3. The crystal also have some porous and crevasses of varying length. The big

size and the well defined shape of the crystals are a consequence of a good crystal growth

process which requires a long time to take place. The crevasses could be the consequence of

natural stress or/and sample preparation. Figure 2b shows SA2 sample (CaO) which present

7
amorphous-like particles. Their edges were not well defined and their shape is rounded.

Furthermore, the inset exposes some relief lines on the particle surfaces (pointed to with arrows).

These lines may have originated during high temperature calcination reaction followed by a

chilling process which produces a thermal shock in the material, creating these fissures on the

surface. The material had many pores and the continuous matrix appearance like it was made of

attached particles. Their size distribution appears homogeneously dispersed around 800 nm.

In the Figure 3c most of the particles are smaller than 1 μm, but the particle size distribution is

broad. Well formed lumps can be observed in Figure 3c were generated during dry-slaked lime

process with water to transform nearly all of the CaO to Ca(OH)2. On the other hand, calcium

hydroxide reacts spontaneously with CO2 forming CaCO3 which is the most stable compound in

the lime cycle. This is the reason some particles with similar morphology were observed in

Figures 2b and 2c. The inset in Figure 2c presents a larger amplification of a particle with some

surface lines (pointed to with arrows) that were generated during crystal growth, thus revealing a

preferential growth direction. The mechanical stress during the hydratation exothermal process

produced cracks in the material volume. The cracks propagation generated a submicron particle

size distribution, as it is described in the following DLS section.

Figure 2

DLS

Figure 3 shows the particle-size distribution of SA3, three different measurements were done:

one when immediately after the agitation process was completed (Figure 3a), the second 15

minutes later (Fig. 3b), and the final one 30 minutes following the first measurement (Fig. 3c)

(Parallel structure). In the first measurement, mayor size particles were identified and the results

8
were: 931.49nm (41 counts), 853.10 (46) and 781.31 (44counts). In the second, particle size

distribution was: 327.48nm (9 counts), 323.83(47), 320.22 (86), 316.65 (100), 313.12 (6) and

309.63 (23 counts). Here it is possible to conclude that when the second measure was made, the

heavier particles had sunk to the bottom of the reservoir and lighter particles contributed to the

size determination. Finally in the third measure, particle sizes were: 133.35nm (48 counts),

100.00 (81), 74.99 (100), 56.23 (57) and 42.17 (24 counts). In this last measure, particles lighter

than those observed in the second measure contributed to the determination of the third particle

size. The lime particle size distribution is important because it influences some properties of

stuccos and mortars such as adhesion, capillarity, porosity and thermal and acoustic diffusivity.

The particle size distribution of lime is smaller than that in OPC. When CaO was hydrated, the

energy generated for the spontaneous-exothermic reaction was realized in a short time. The

relatively short time of energy liberation caused the violent reaction and small portions of

reacting material exploded producing Ca(OH)2 with a submicron particle-size distribution.

Figure 3

ICP-MS

Table 1 summarizes results of heavy metals content after ICP-MS analyses. Pb quantification

was established exactly by this technique, contrasting with the result obtained through AAS,

where the determination was noted just as under the quantification limit. The variation of

vanadium content between SA2 and SA3 was relevant, with less content in SA1 before the

addition of water to hydratation process.

Table 1

9
FT-IR

The usefulness of qualitative analysis from the characteristic frequencies provides information to

identify chemical constituents in a compound. Infrared spectra narrow the options to a few

specific crystals if only one or two compounds are present. Additionally, a correlation of FTIR

and XRD may be helpful. Figure 4a shows the FTIR bands of SA1. The relatively low intensity

band at 3628 cm-1 corresponded to O─H bond matching with a low concentration of Ca(OH)2 in

the sample. The hydroxide is a remaining component of the carbonation process. The bands at

1444, 877 and 713 cm-1 correspond to the three different elongation modes of C─O bonds while

the bands at 2980, 2875, 2513 and 794 cm-1are harmonic vibration of these elongation modes.

The width of this band implies that O─H groups must be forming hydrogen bridges. The minor

bands at 2875 cm-1 and the first overtone at 2990 cm-1 corresponds to C═O from carbonate ion.

The thin and intense band at 1795 cm-1 is also associated to the carbonate C═O bonds. The very

strong band at 1444 cm-1 is related to the carbonate C─O bonds. The bands at 1105, 1018 and

790 cm-1 are related to SiO2 (Quartz), confirmed by the previous XRD analyses. The band at 713

cm-1 is related to Ca─O bonds. Comparing the spectra from a CaCO3 standard (Baker analyzed

99.9%) with the SA1 spectra, the intense and sharp band at 877 cm-1 is assigned to CaCO3.

While the comparison between sample and standard spectra, confirm very close similarity.

Figure 4b shows the spectrum of SA2 and comparison with standard of CaO spectrum. The

strong band at 3643 cm-1 corresponds to the O─H bonds from the remaining hydroxide (Park et

al. [12]). The band at 1417 cm-1 band corresponds to C─O bond. The band centered at 866 cm-1

corresponds to C─O bond. The wide and strong band at around 500 cm-1 corresponds to the

Ca─O bonds. This band is the largest one in the CaO standard spectrum, but it rather smaller in

the SA2 spectrum.

10
Figure 4c shows the SA3 and Ca(OH)2 standard spectra. The strong band at 3643 cm-1 is related

to the O─H bond from hydroxides. The band at 1795 cm-1 corresponds to C═O bonds from

carbonate. The intense and wide band at 1427 cm-1 corresponds to C─O bonds from carbonate.

The band at 875 cm-1 corresponds to Ca─O bonds. The weak band at 1126 cm-1 corresponding to

S─O bonds which reveals the presence of sulfur. This pollutant was possibly added by gases

from the fuel oil combustion during the calcination process. The band in the region of 500 cm-1

corresponds to Ca═O bonds, possibly derived from the partial hydratation process. The CaCO3

was collected from a Mexican mine and it was transformed to CaO through a calcination

reaction. This reaction had a low efficiency and consequently the CaO obtained had a

considerable amount of CaCO3 along with small amounts of the other minerals. These secondary

minerals were not transformed either by the calcination reaction or the subsequent reactions. Fuel

combustion produced gases during calcination reaction and this may generate sulfur

contamination depending on the fuel quality. If a fuel rich in sulfurated organic compounds was

used, the CaO produced would have more sulfur contamination. All the standard spectra closely

matched with spectra samples, demonstrating that the process produces a loop cycle.

Figure 4

Conclusions

The aforementioned techniques offer a complete characterization of the lime cycle and this

information can be used for new applications where lime is used, such as construction,

restoration, food additives and others. It was possible to confirm how the different materials in

each cycle stage were changing to form the most stable compound CaCO3. This last stage is

evidence that the lime cycle is dynamic and transitions occur spontaneously. The process to

11
produce Ca(OH)2 from CaCO3 has influence in the morphological and topological features of

lime particles. According to the X-ray diffraction patterns, it was possible to identify each one of

the crystalline phases of these materials. This is important in the industry because it allow the

identification of any phase. In the construction industry, the X-ray diffraction patterns permits

the identification of these phases in mortars, stuccos and plasters. SEM images are a powerful

tool to study the crystalline growth habits, and also morphology and topology of the kinetic

phases in lime cycles. DLS for Ca(OH)2 proved that the particle size distribution is in the

submicron range, indicative of lime can be used to reduce the porosity of compound materials

used in the construction industry. FTIR allows for the determination of specific bonds of

molecules, and to identify any phase of the lime cycle in compound materials. For restoration

purposes, this technique is ideal because allows for phase identification with a small sample

which means a non-destructive sampling of historical buildings. AAS and ICP are especially

good techniques for a precise determination of chemical elements of contaminants for any stage

of the lime cycle. It can also be used in the restoration to permit reformulation of the original

materials used. It is important to take into consideration that all these techniques are fundamental

in the use of lime as a food additive, because it agree to contaminants detection.

Acknowledgements

This work was developed with the generous collaboration of several people and organizations:

technical support: Carolina Muñoz, Alicia del Real, Ofelia Pérez, Genoveva Hernandez, along

with support of: CoSDAC-SEP PROJECT 022.09-P03, and FIFI-UAQ to whom we express our

sincere gratefulness.

12
References

Boynton, R.S. (1980). Chemistry and technology of lime and limestone. Ed. John Wiley & Sons,

USA.

Delatte, N. J. (2201). “Lessons from Roman Cement and Concrete”. J. Profl. Issues in Engrg.

Educ. and Pract., 127(3), 109-115.

Galván-Ruiz, M., Baños, L. and Rodríguez-García M.E. (2007). Lime characterization as a food

additive. Sens. & Instrumen. Food Qual. (1),169–175.

Galván-Ruiz, M., Velázquez-Castillo, R., Pérez-Lara, M., Arjona, J.L., Baños, L. and Rodríguez-

García M.E. (2009). Chemical and physical characterization of stuccos from a Mexican colonial

building: “El Museo del Calendario” of Querétaro. Archaeometry. (51), 000–000.

Hill, N., Holmes, S., and Mather, D. (1992). Lime and other alternative cements. Ed.

Intermediate Technology Publications, U.K.

Holmes, S., and Wingate, M. (2003). Building with lime, revised edition, Ed. ITDG Publishing,

U.K.

Keum, D., Naka, K., and Chujo, Y. (2003). “Unique crystal morphology of hydrophobic CaCO3

composite by sodium trisilanolate in a mixture of a water-miscible organic solvent and water”.

Journal of Crystal Growth (259), 411–418.

Park, J., Min, D. and Song, H. (2002). “Structural Investigation of CaO–Al2O3 and CaO–

Al2O3–CaF2 Slags viaFourier Transform Infrared Spectra”. ISIJ International, 42(1), 38–43.

13
Figure captions

Figure 1. XRD patters of a) SA1, b) SA2 and c) SA3. C-calcite, Q-quartz, M-muscovite, K-

kaolinite, P-portlandite, O-calcium oxide and S-calcium silicate.

Figure 2. SEM micrographs of a) SA1, b) SA2 and c) SA3. In all images, the morphology of

particles and the porosity of the different materials can be observed.

Figure 3. Particles size distribution of SA3. Measures were done a) immediately when dilution in

bi-distilled water was finished, b) 15 min after first measure and c) 30 min after first measure.

Figure 4. FTIR spectra of a) SA1 and CaCO3 standard; b) SA2 and CaO standard, and c) SA3

and Ca(OH)2 standard. Solid lines correspond to samples and dot lines correspond to standards.

In some bands, their corresponding vibrating groups are shown.

14
Table Captions

Table 1. ICP-MS analyses of SA1, SA2 and SA3. Pb quantification can be done.

Table 1

Li
Sample Be V Cr Co Ni Cu As Se Cd Tl Pb
mg/kg
SA1 1.3669 0.0 1.0211 0.0481 1.2674 2.3924 0.6621 0.4008 0.0 0.0 0.0536 0.8076
SA2 0.0087 0.0 1.9068 0.1066 0.0686 1.4785 0.2742 0.0290 0.0 0.0 0.0 0.0012
SA3 0.3401 0.0 4.3403 0.2150 0.0884 1.1589 0.1932 0.0849 0.0 0.0 0.0 0.0527

15
Figure 1

16
Figure 2

17
Figure 3

18
Figure 4

19