ACI MATERIALS JOURNAL

Title no. 104-M45

TECHNICAL PAPER

Characteristics of Cement Mortar with Nano-SiO2 Particles

by Byung-Wan Jo, Chang-Hyun Kim, and Jae-Hoon Lim
The amorphous or glassy silica, which is the major component of a pozzolan, reacts with calcium hydroxide formed from calcium silicate hydration. The rate of the pozzolanic reaction is proportional to the amount of surface area available for reaction. Therefore, it is plausible to add nano-SiO2 particles (NS) to make high-performance concrete. The compressive strengths of cement mortar were evaluated at various water-cementitious material ratios (w/cm). Five different w/cm were used, including 0.23, 0.25, 0.32, 0.35, and 0.48 and four contents of NS, 3, 6, 9, and 12% by weight of cement. The compressive strengths of cement mortar with the addition of silica fume were also evaluated at a w/cm of 0.35 to compare with mortar containing nano-SiO2 particles and three contents of silica fume were: 5, 10, and 15% by weight of cement. The experimental results show that the compressive strengths of mortars with NS were all higher than those of mortars containing silica fume at 7 and 28 days. It was demonstrated that the nano-particles were more valuable in enhancing strength than silica fume. This paper also analyzes some available examinations to monitor the hydration progress continuously, such as SEM observation, residual quantity test for Ca(OH)2, and the rate of heat evolution. The results of the examinations indicate that the SiO2 in nano scale behave not only as a filler to improve the microstructure, but also as an activator to promote pozzolanic reactions.
Keywords: compressive strength; pozzolanic reactions; silica fume.

component of a pozzolan, reacts with calcium hydroxide formed from the hydration of calcium silicates. The rate of the pozzolanic reaction is proportional to the amount of surface area available for reaction. Therefore, it is feasible to add nano-SiO2 of a high purity (99.9%) and a high Blaine fineness value (50 m2/g [244,077 ft2/lb]) to improve the characteristics of cement mortars. RESEARCH SIGNIFICANCE The nano scale of particles can result in dramatically improved or different properties from conventional grain-size materials of the same chemical composition. Accordingly, the use of nano-SiO2 in particle form with 99.9% of SiO2 in nano scale was considered in this paper to compare with the influences of silica fume in micro scale in cement mortar. EXPERIMENTAL PROCEDURE Materials The addition of finely ground solid materials to portland cement is an established practice in modern cement technology. Silica fume has been used either as a partial replacement for cement or as an additive when special properties are desired. The most frequently specified property has been a minimum silicon dioxide (SiO2) content, with values ranging from 85 to 95% being typical and moisture content with a maximum of 3.0%, and a specific surface area with minimum of 20 m2/g (97,630 ft2/lb) at a bed porosity of 50%. Accordingly, silica fume used in this study was in powder form with 95% of SiO2 and a particle size of 0.1 m to compare with the influences of nano-SiO2 in cement mortar. A cement paste is made up of small grains of hydrated calcium silicate gels, nanosized individual pores, capillary pores, and large crystals of hydrated products. There should be room for nanophase materials to improve the properties of pure cement paste.7 In view of the abovementioned, nano-SiO2 in particle form with 99.9% of SiO2 and in particle size of 40 nm was used. The cementitious materials used are ordinary portland cement (OPC), silica fume powder (SF), and nano-SiO2 particles (NS), their pertinent chemical and physical properties, as provided by Sanghyeon nanophase material company in Korea, are given in Table 1. Particle morphologies and x-ray diffraction (XRD) diagrams of silica fume and nano-SiO2 are shown in Fig. 1 and 2. The high-range water-reducing admixture, a polycarboxylate with a relative density of 1.06, was incorporated in all mixtures; the content was adjusted for each mixture to ensure that no segregation would occur. For mortar mixtures, cement and regular sand with a maximum size of 4.76 mm
ACI Materials Journal, V. 104, No. 4, July-August 2007. MS No. M-2006-273 received July 6, 2006, and reviewed under Institute publication policies. Copyright 2007, American Concrete Institute. All rights reserved, including the making of copies unless permission is obtained from the copyright proprietors. Pertinent discussion including authors closure, if any, will be published in the May-June 2008 ACI Materials Journal if the discussion is received by February 1, 2008.

INTRODUCTION Recently, nano technology has attracted considerable scientific interest due to the new potential uses of particles in nanometer (109 m) scale. The nano-scale size of particles can result in dramatically improved properties from conventional grain-size materials of the same chemical composition. Thus, industries may be able to reengineer many existing products and to design new and novel products that function at unprecedented levels. There are few reports on mixing nano-particles in cement-based building materials.1-6 Li et al.1 investigated cement mortars with nano-SiO2 or nano-Fe2O3 to explore their super mechanical and smart (temperature and strain sensing) potentials. The Fuji Chimera Research Institute4 addressed functional applications of SiO2 in nano scale. Up until now, however, research performed over the years has been largely aimed at achieving high mechanical performance with cement replacement materials in micro size. Lu and Young5 obtained an 800 MPa (116,030 psi) strength on compressed samples, and Richard and Chyrezy6 developed reactive powder concretes with compressive strength (RPCs) ranging from 200 to 800 MPa (29,007 to 116,030 psi) and fracture energies up to 40 kJ m2. The development of an ultra-highstrength concrete was made possible by the application of a densified system containing homogeneously arranged ultrafine particles (DSP) with high-range water-reducing admixture and silica fume content. In view of these advances, the aim of this study is to investigate the influences of nano-SiO2 in cement mortars. The amorphous or glassy silica, the major 404

ACI Materials Journal/July-August 2007

ACI member Byung-Wan Jo is a Professor, Department of Civil Engineering, Hanyang University, Seoul, Korea. He received his BS from Hanyang University, Seoul, Korea; his MS from Ohio University, Athens, Ohio; and his PhD from University of Florida, Gainsville, Fla. Chang-Hyun Kim is a PhD Candidate of civil engineering, Hanyang University. Jae-Hoon Lim is an MS Candidate of civil engineering, Hanyang University.

Table 1Chemical composition and physical properties of cementitious materials

Chemical composition, % Items SiO2 Al2O3 Fe2O3 CaO MgO SO3 LOI Specific gravity Average particle size Ordinary portland cement 22.0 6.6 2.8 60.1 3.3 2.1 2.6 Physical properties 3.15 13 m 0.38 2.33 0.1 m 20 40 nm 50 Silica fume 95.0 0.9 0.6 0.3 0.9 0.5 2.1 Nano-SiO2 99.9 0.1

Fig. 1Particle morphologies: (a) silica fume; and (b) nano-SiO2.

SSA, m2/g

Table 2Mixture proportion of specimens

Name of w/cm, Water, Cement, Sand, Silica Nano- HRWRA, specimens % g g g fume, g SiO2, g % OPC SF5 SF10 SF15 NS3 NS6 NS9 35 89.25 255 242.3 229.5 216.8 247.3 239.7 232.0 224.4 625.0 12.8 25.5 38.3 7.7 15.3 23.0 30.6 1.2 1.9 2.1 2.2 1.8 2.4 2.9 3.3

Fig. 2XRD analyses: (a) silica fume; and (b) nano-SiO2. (3/16 in.) was mixed with the ratio 1:2.45. The specific gravity of the regular sand was 2.6, the fineness modulus was 2.7, and the absorption capacity was 1.5%. The sand was graded as per ASTM C 33. Additional water was added to the mortar mixtures to satisfy the saturated surface-dry condition of the aggregate. Mixture proportions Details of the mixture proportions for the mortar containing different levels of silica fume and nano-SiO2 are given in Table 2. Five different water-cementitious material ratios (w/cm) were used including 0.23, 0.25, 0.32, 0.35, and 0.48 and four contents of NS of 3, 6, 9, and 12% by weight of cement. The compressive strengths of cement mortar with the addition of silica fume were also evaluated at a w/cm of 0.35 to compare with mortar containing NS and three contents of silica fume were 5, 10, and 15% by weight of cement. The dosage of high-range water-reducing admixture was shown as a percentage of the weight of the cementitious materials and adjusted according to the effect of the different levels of silica fume and NS. In all mixtures, the amount of highrange water-reducing admixture used was sufficient such that no bleeding or segregation was reported. Testing procedure The cement mortars were mixed in a rotary mixer. Nanoparticles are not easy to disperse uniformly due to their high surface energy. Accordingly, defoamer and dispersant agent were (if applicable) dissolved in water and then mixing was performed as follows: 1. The NS were stirred with the mixing water at high speed (120 rpm) for 1 minute; ACI Materials Journal/July-August 2007

NS12

Notes: OPC equals ordinary portland cement mortar; SF equals cement mortars containing silica fume (5, 10, and 15%); NS equals cement mortars containing nano-SiO2 (3, 6, 9, and 12%); and HRWRA equals high-range water-reducing admixture.

2. The cement and silica fume (if applicable) were added to the mixer and mixed at medium speed (80 rpm) for another 30 seconds; 3. Mixing at medium speed, the sand was added gradually; 4. The high-range water-reducing admixture was added and stirred at high speed for additional 30 seconds; and 5. The mixture was allowed to rest for 90 seconds and then mixed for 1 minute at high speed. For each mixture, six cubic specimens of 50 x 50 x 50 mm (1.97 x 1.97 x 1.97 in.) were made for compressive strength. After being demolded at the age of 1 day, all specimens were cured in water at 77 1.8 F (25 1.67 C) for 7 and 28 days. The cubes were tested for compression using a universal testing machine under load control at 0.24 MPa/second (34.81 psi/second). The SEM observations were analyzed, the residual quantity test for Ca(OH)2 was conducted, and the rate of heat evolution with differential calorimetric analysis was estimated to monitor the hydration process of cement pastes. EXPERIMENTAL RESULTS AND DISCUSSION Microstructure To verify the mechanism predicted by the compressive strength test, scanning electron microscope (SEM) examinations were performed. Additions of NS were found to influence hydration behavior and led to differences in the microstructure of the hardened pastes. Figures 3 and 4 are SEM micrographs of cement pastes with and without nano-SiO2 at 7 days. Fracture surface of OPC paste with 7 days hydration showed ettringite needles growing into water-filled pore space, platey 405

Table 3Cumulative heat evolution for 72 hours

Ordinary portland cement 231.1, J/g SF10 233.7, J/g NS10 238.5, J/g

Notes: SF equals cement containing silica fume (10% by weight); and NS equals cement containing nano-SiO2 (10% by weight).

Table 4Compressive strength (MPa) of control specimens at same w /cm

7 days OPC 38.26 38.64 40.22 41.61 38.87 40.19 43.76 48.74 SF5 SF10 SF15 NS3 NS6 NS9 NS12 28 days 44.64 43.89 47.12 50.47 47.85 50.67 51.37 58.13

Fig. 3Scanning electron microscope micrograph of ordinary portland cement paste.

Fig. 4Scanning electron microscope micrographs of paste containing nano-SiO2 particles.

continues to hydrate rapidly, reaching a maximum rate at the end of the acceleration period (Stage 3), which corresponds to the maximum rate of heat evolution. Thereafter, the reaction rate again slows down (Stage 4) until it reaches a steady state. The amounts of heat evolved from the different mixtures in 72 hours are 238.5 J/g (NS10), 233.7 J/g (SF10), and 231.1 J/g (OPC). These results indicate that the addition of nano-SiO2 increases the amount of heat evolved during the setting and hardening of the cement. A greater dosage of high-range water-reducing admixture, however, retards the early hydration of the cement paste containing nano-SiO2. Heat-treating is necessary to accelerate the early hydration and the pozzolanic reaction. Residual quantity of calcium hydroxide The extent of a pozzolanic reaction can be followed by monitoring the decrease in calcium hydroxide. The amorphous or glassy silica reacts with calcium hydroxide formed from calcium silicate hydration. From quantitative analysis at 7 days, the contents of Ca(OH)2 remaining in the pastes were 4.56% (NS10), 6.09% (SF10), and 6.89% (OPC). The main effects of pozzolanic reaction are strength development and smaller pore-size distribution. Compressive strength Hypothesis testing is used in this study to verify the increase in strength. The theory of a statistical test of hypothesis is to enable the researcher to either reject or accept the null hypothesis with a measured risk , which is often referred to error of estimation; 5% error of estimation or 95% confidence level will be used in this study. More details on this statistical analysis are given elsewhere.8,9 The development of compressive strength with an age of 7 and 28 days was shown in Table 4. It can be seen that the compressive strength development of a mortar mixture containing NS were all higher than that of the control cement mortars with the same w/cm of 0.35. The difference of strength development in mortars can be attributed to pozzolanic reactions. As mentioned previously, nanoparticles are thought to be more effective in pozzolanic reaction than silica fume. Also, the nano-SiO2 would fill pores to increase the mortar strength, as silica fume does. Therefore, it is confirmed that the addition of nano-SiO2 to cement mortars improves their strength characteristics. Compressive ACI Materials Journal/July-August 2007

Fig. 5Calorimetric curves of heat evolution. crystals of CH and C-S-H with indeterminate morphology (Fig. 3). On the other hand, the microstructure of the mixture containing nano-SiO2 revealed a dense, compact formation of hydration products and a reduced number of Ca(OH)2 crystals (Fig. 4). The rate of heat evolution The fineness of grinding is important in the rate of heat evolution. Finely-ground cements increase the hydration rate. The heat of hydration may be defined as the amount of heat evolved during setting and hardening. Figure 5 compares the heat evolution rates of NS10 with NS (10% of cement weight), OPC, and SF10 with silica fume (10% of cement weight). When mixed with water, a period of rapid heat evolution occurs (Stage 1). This is followed by an inactive period of the induction or dormant stage (Stage 2), which is the reason why cement remains in the plastic state for several hours. By the end of the induction period, C3S has begun to react again with renewed vigor. The silicate 406

Table 5Strength of specimens containing nano-SiO2 particles

Compressive strength, MPa Material w/cm, % 0.23 0.25 0.32 0.35 0.48 0.23 0.25 0.32 0.35 0.48 Cement mortar 0.23 0.25 0.32 0.35 0.48 0.23 0.25 0.32 0.35 0.48 0.23 0.25 0.32 0.35 0.48 NS, % 0 0 0 0 0 3 3 3 3 3 6 6 6 6 6 9 9 9 9 9 12 12 12 12 12 HRWRA, % 3.92 3.84 1.71 1.19 0 4.26 4.18 2.30 2.05 0.68 5.12 4.95 3.24 2.90 0.94 5.80 5.63 3.75 3.50 1.36 6.48 6.39 4.01 3.92 1.71 7 days 69.26 56.23 44.56 38.26 25.93 74.34 58.70 45.06 38.87 29.74 88.16 64.66 47.02 40.19 31.52 80.87 74.72 50.23 43.76 32.51 78.53 67.15 53.25 48.74 37.09 28 days 78.58 72.81 58.27 44.64 32.64 87.84 77.95 59.65 47.85 38.27 102.28 91.09 60.71 50.67 41.57 97.48 97.27 65.63 51.37 44.24 92.85 91.62 69.16 58.13 46.54

Notes: NS equals nano-SiO2; and HRWRA equals high-range water-reducing admixture.

strength of cement mortars with nano-SiO2 as a function of w/cm are summarized in Table 5 and Fig. 6. At all w/cm between 0.23 and 0.48, the strength of the mortar was found to increase as the nano-SiO2 content increased from 3 to 12%. It should be noted, however, that using a higher content of nano-SiO2 must be accompanied by adjustments to the water and high-range water-reducing admixture dosage in the mixture to ensure that specimens do not suffer excessive self desiccation and cracking. Otherwise, using this much quantity of nano-SiO2 could actually lower the strength of composites instead of improving it, although this finding was not observed in this study. The result of this study has shown that 12% nano-SiO2 has no adverse effect on strength, but this percentage cannot be considered as the optimum level for maximizing strength. In this study, it has been suggested that the optimum nano-SiO2 content should be 6% at a w/cm of 0.23. FURTHER RESEARCH The development of an ultra-high-strength concrete would be made possible by the application of DSP with high-range water-reducing admixture and nano-SiO2 content. In view of these advances, the aim of future research is to develop an ultra-high-strength powder concrete. CONCLUSIONS Based on the results of the compressive strength test, it is expected that nano-scale SiO2 behaves not only as a filler to improve mortar cement microstructure, but also as a promoter of pozzolanic reaction. To verify these mechanisms predicted, the authors have analyzed the hydration process

Fig. 6Compressive strength of specimens containing nano-SiO2 particles: (a) 7 days; and (b) 28 days. using three types of cement mortars. Results are consistent with the strength enhancement expected. Therefore, it is effective to add NS to cement mixtures for introducing high strength to concrete. ACKNOWLEDGMENTS
The authors acknowledge the financial support from the Korea Ministry of Construction and Transportation.

REFERENCES
1. Li, H.; Xiao, H. G.; Yuan, J.; and Ou, J., Microstructure of Cement Mortar with Nano-Particles, Composites Part B: Engineering, V. 35, No. 2, Mar. 2003, pp. 185-189. 2. Lau, A. K.-T., and Hui, D., The Revolutionary Reaction of New Advanced MaterialsCarbon Nanotube Composites, Composites Part B: Engineering, V. 33, No. 4, June 2002, pp. 263-277. 3. Bauer, B. J.; Liu, D.; Jackson, C. L. et al., Epoxy/SiO2 Interpenetrating Polymer Networks, Polym. Adv. Technol., 1996, pp. 333-339. 4. Fuji Chimera Research Institute Inc., Fine (Impalpable) Powder Market 2002Present and Future Outlook, 2002. 5. Lu, P., and Young, J. F., Hot Pressed DSP Cement Paste, Material Research Society Symposium Proceedings, No. 245, 1992, pp. 321-328. 6. Richard, P., and Chyrezy, M. H., Reactive Powder Concretes with High Ductility and 200-800 MPa Compressive Strength, Concrete Technology Past, Present, and Future, Proceedings of the V. Mohan Malhotra Symposium, SP-144, P. K. Mehta, ed., American Concrete Institute, Farmington Hills, Mich., 1994, pp. 507-528. 7. Qing, Y., Research on the Comparison of Pozzolanic Activity between Nano SiO2 and Silica Fume, Concrete, Mar. 2001, pp. 19-22. 8. Mendenhall, V.; Scheaffer, R. I.; and Wackerly, D. D., Mathematical Statistics with Applications, Duxbury Press, Second Edition, 1981, 390 pp. 9. Ang, A. H.-S., and Tang, W. H., Probability Concepts in Engineering Planning and Design, John Wiley & Sons, 1975, 244 pp.

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