Effect of Nano-sized Titanium Dioxide on Early Age Hydration of Portland Cement

A.R. Jayapalan, B.Y. Lee, and K.E. Kurtis1

Abstract. The effect of nano-scale non-reactive anatase titanium dioxide (TiO2) on early age hydration of cement was experimentally studied. Isothermal calorimetry was performed on cement pastes with two different particle sizes of TiO2 at replacement levels of 5, 7.5 and 10%. The addition of TiO2 to cement increased the heat of hydration and accelerated the rate of reaction at early stages of hydration. This increase was found to be proportional to the percentage addition and the fineness of TiO2. These results demonstrate that the addition of non-reactive nanoscale fillers could affect the rate of cement hydration by heterogeneous nucleation.

1 Introduction
The early age hydration of Portland cement remains of interest to researchers and to industry because of potential implications relating to setting time, dimensional stability and strength development. Researchers have noted an acceleration of cement hydration when fine fillers are added to cement [1, 2]. It has been observed that fine (0.5m to 4m) powders of limestone [3], quartz [4], silica fume [5] and pulverized fly ash [6], when added up to 15% cement replacement levels, can increase the rate of the cement hydration. Addition of a fine non-reactive filler to cement modifies the hydration rate primarily due to dilution, modification of particle size distribution and heterogeneous nucleation [4]. For increasing dosage rates of inert filler (when used as a partial
A.R. Jayapalan Georgia Institute of Technology e-mail: amalrajpj@gatech.edu B.Y. Lee Georgia Institute of Technology e-mail: blee30@gatech.edu K.E. Kurtis Georgia Institute of Technology e-mail: kimberly.kurtis@ce.gatech.edu

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replacement of cement), cement dilution results in an increase of the water-tocement ratio (w/c) and a decrease in total cement content when water-to-solids ratio (w/s) is kept constant. The modification of particle size distribution due to chemically inert filler addition changes the system porosity, but the effect on cement hydration does not seem to be well documented in literature. The surface of the fine fillers has been shown to provide sites for nucleation of cement hydration products (C-S-H) and catalyzes the reaction by reducing the energy barrier [4]. The effectiveness of this catalysis depends on fineness and dosage of the filler [4]. In addition, other phenomena may occur, including water ab/adsorption by the nanoparticles, interactions with nanoparticle surface treatments, and reaction of materials previously presumed to be inert. Most of the fine fillers previously examined react chemically to some extent in the cement hydration process. Limestone may be slightly reactive with the Portland cement forming a monocarbonate phase [3]. Silica fume reacts with calcium hydroxide by pozzolanic reaction. Considering the increasing interest in inert additives to cement, such as titanium dioxide (TiO2), there needs to be a study that directly focuses on the effect of non-reactive filler on cement hydration. Titanium dioxide (TiO2) is added as a filler to cement for its photocatalytic activity. Research has shown that the photocatalytic activity is superior in nano-crystalline TiO2 and that it exhibits maximum efficiency in anatase phase compared to rutile or brookite phase [7, 8]. When added to Portland cement, TiO2 is considered to act as inert filler and has not been believed to take part in the hydraulic reaction of Portland cement. The nano-size of the TiO2 particles could significantly affect the rate of hydration reaction especially in the early stages. Most of the previous researches on the effect of fine inert fillers on cement hydration were conducted using micrometer sized particles in the range of 0.5m to 4m. Jo et al. used nano-particles (of average particle size 40nm) of silicon dioxide (SiO2) [9], but SiO2 could react with cement during early hydration due to its high pozzolanic activity. Thus, the objective of this research was to better understand the effect of addition of nano-sized and presumably non-reactive anatase TiO2, on the early hydration of Portland cement. Specifically, the effects of variation particle size and percentage addition of TiO2 nanoparticles were examined as a part of this research. Isothermal calorimetry was used to characterize the influence of these factors on early age cement hydration.

2 Research Methodology 2.1 Materials

Six blended cements were prepared and examined to study the effect TiO2 dosage rate and particle size on the cement hydration process. The potential Bogue composition of the ordinary Portland cement used for making all TiO2blended

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cement was 51.30% C3S, 19.73% C2S, 8.01% C3A and 9.41% C4AF and 0.40% Na2Oeq. Two TiO2 powders (T1 and T2), of different surface areas were labblended with ordinary Portland cement, each at 5, 7.5 and 10% replacement by mass. The properties of the TiO2 powders, obtained from Millennium Inorganic Chemicals are given in Table1.
Table 1 Properties of anatase TiO2 added to cement (as obtained from the manufacturer)
Crystal Size (nm) T1 T2 20-30 15-25 Agglomerate Size (m) 1.5 1.2 Surface Area (m /g) pH 45-55 75-95 3.5-5.5 3.5-5.5
2

Purity (%) >97 >95

2.2 Sample Preparation

A w/s of 0.50 was used for all the mixes. The mixing tools and materials were stored at a constant temperature of 23C for 24 hours before mixing. TiO2 powder was added to the water and mixed using a handheld mixer for 60 seconds to disperse the agglomerates. The cement was then added, mixed by hand using a stirrer for a maximum of 10 seconds and mixing continued with the handheld mixer. The entire mixing period was maintained within 605 seconds. The paste was then carefully poured into calorimeter capsules and the weight of the cement paste in the capsule is noted.

2.3 Methods
Isothermal calorimetry was performed on triplicate paste samples using an eight channel micro-calorimeter at 25C. The capsules were placed inside the isothermal calorimeter within 240 seconds of addition of cement to water. The time of addition of cement to water is considered as the starting time for each sample. The data for initial 10 minutes of the tests was discarded to ensure that capsule reached thermal equilibrium with the calorimeter. The rate of hydration was measured every 60 seconds as power (mW) and was normalized per gram of cement. Since the difference between the triplicate samples was not significant, one of the triplicate samples per mix was chosen for the comparative studies.

3 Results and Discussion

Isothermal calorimetry was carried out on the laboratory blended TiO2-cements to study the effect of TiO2 replacement level and particle size on the early hydration reaction. The data for the first 48 hours, starting from the time of mixing of cement and water, was analyzed.

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3.1 Rate of Hydration of TiO2-Blended Cements

Figure 1 shows the variation of the rate of hydration of ordinary Portland cement and the TiO2-blended cements at 5, 7.5 and 10% replacement levels. For the graph of ordinary Portland cement, the main peak of heat release corresponding to the reaction of C3S can be observed from ~1 to ~8 hours. This main peak is followed by a secondary peak corresponding to C3A hydration. From Figure 1 it can be observed that all the mixes with TiO2 addition showed accelerated hydration compared to ordinary Portland cement. For example, at 10% replacement, the peak of C3A hydration was accelerated by around 80 and 180 minutes for the mixes with T1 and T2 respectively compared to the ordinary Portland cement. The increasing dosage of TiO2 was found to accelerate the rate of hydration of the mixes and increase the peaks for C3S and C3A hydration. For instance, the increase in the peak of the C3A hydration compared to the control mix was found to be 22.24%, 28.32% and 37.20% for the mixes with 5%, 7.5% and 10% replacement by T2. These results indicate that heterogeneous nucleation effect could be more dominant than dilution effect. Previous research using calorimetry has also shown that heterogeneous nucleation increases the rate of cement hydration when fine inert materials are added to Portland cement [4]. From Figure 1 it can also be observed that the rate of hydration for the cement mixes prepared by replacement with finer TiO2 (T2) was higher than all the mixes

8 OPC 7
T2 - 10%

T1 - 5% T1 - 7.5%

6 Power (mW/g)
T1 - 10%

5 4 3 2
OPC

T1 - 10% T2 - 5% T2 - 7.5% T2 - 10%

1 0 0 10 20 30 Time (hours) 40 50

Fig. 1 Rate of hydration of TiO2-blended cements

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prepared with coarser TiO2 (T1). This shows that the rate of cement hydration in the presence of TiO2 strongly depends on the size (Table1) of the nano-sized particles that are blended to the cement, with smaller particles accelerating the reaction much more than larger particles. This reinforces the conclusion that nucleation effect, which depends on the surface area of the particles, could be dominant than dilution effect in the case of addition of nano-TiO2 particles to cement.

3.2 Cumulative Energy Released by TiO2-Blended Cement

Figure 2 shows the variation of cumulative energy released with time of ordinary Portland cement and the lab-blended TiO2 cements. For the graph of ordinary Portland cement it can be seen that after the initial dormant period there is a rapid increase in the total energy released, which corresponds to the peaks of C3S and C3A hydration. From Figure 2 it can be seen that the total energy evolved during the hydration reaction increased as the percentage replacement of cement with TiO2 was increased. The total energy released also increased with the increasing surface area of TiO2 used, again reinforcing the significant effect of the addition of nano-sized particles in the nucleation reaction.
350
T1 - 10%

300 Energy (Joules/g) 250 200 150 100 50 0 0 10

T2 - 10%

OPC T1 - 5%
OPC

T1 - 7.5% T1 - 10% T2 - 5% T2 - 7.5% T2 - 10%

20

30 40 Time (hours)

50

60

Fig. 2 Cumulative energy released by OPC and TiO2-blended cements

As explained earlier, the addition of TiO2 to cement paste affects the hydration rate by dilution effect and heterogeneous nucleation. With increased dosage of fine filler, the rate of hydration of cement and the total heat evolved will be decreased by the dilution effect and increased by nucleation effect. In all the tests

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that were conducted in this research it was observed that increasing the dosage and lowering of particle size of filler caused the rate of reaction to increase (Figure 1). Figure 2 shows that at all replacement rates by TiO2 the cumulative heat evolved is greater than that of ordinary cement paste indicating an acceleration of cement hydration. This suggests that the heterogeneous nucleation effect is the dominant effect than dilution effect when nano-sized TiO2 particles are added to cement. It should be noted here that the TiO2 used for these experiments were acidic, presumably due to surface treatments used in their manufacturing. The dissolution of surface groups (chlorides, sulphates or ammonium ions) could affect the rate of reaction of the cement particles which are in a highly basic environment during normal hydration. Research on the effect of the acidity and surface coating of TiO2 particles on the rate of nucleation is needed. It is our understanding, however, that titania blended with portland cement in commercial use is not further processed to remove or alter the surface chemistry; that is, the TiO2 examined herein should be quite similar to that used in practice.

4 Conclusions
The effect of the addition of nano-sized TiO2 particles on the early hydration reaction of cement was studied as a part of this research. When TiO2 of different particle sizes were added to cement, the hydration reaction was accelerated and the rate of hydration increased. The increase in the rate of reaction was proportional to the dosage of the TiO2. Smaller particles of TiO2 were found to accelerate the reaction more than larger particles. Heterogeneous nucleation effect was found to be dominant compared to the effect of dilution when inert TiO2 particles were added to cement.
Acknowledgments. This research is supported by the National Science Foundation under Grant Nos. CMMI-0825373 and CMMI-0855034. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.

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6. Gutteridge, W.A., Dalziel, J.A.: Filler cement: The effect of the secondary component on the hydration of Portland cement: Part 2: Fine hydraulic binders. Cement Concrete Res. 20(6), 853861 (1990) 7. Tanaka, K., Capule, M.F.V., Hisanaga, T.: Effect of crytallinity of TiO2 on its photocatalytic action. Chem. Phys. Lett. 187(1-2), 7376 (1991) 8. Bianchi, C.L., et al.: The role of the synthetic procedure of nano-crystalline TiO2 on the photodegradation of toluene. In: International RILEM Symposium on Photocatalysis, Environment, and Construction Materials - TDP 2007. Rilem Publications, Florence (2007) 9. Jo, B.W., et al.: Characteristics of cement mortar with nano-SiO2 particles. Constr. Build. Mater. 21(6), 13511355 (2007)