INVESTIGATIONS ON THE EFFECT OF NANOSILICA ON THE PERFORMANCE OF CEMENT

S. Harsh, A. K. Arora, M M Ali and M Vasudeva National Council for Cement and Building Materials, New Delhi ABSTRACT The paper presents the results from ongoing investigations at National Council for Cement and Building Materials on the effect of nanosilica on the performance of cements. The addition of nanosilica is reported to result in improvements in both compressive and flexural strengths of cement mortar. Nanosilica of average particle size of 15nm was blended with two samples of ordinary Portland cement. The nanosilica addition was varied in the range of 2-5 percent, replacing equal mass of control OPC. The resultant blends were investigated for their physical properties. For comparison purpose blends of 5 and 10 percent microsilica with control OPC samples were also prepared and evaluated along with above nanosilica-blends and the control OPC samples. Nanosilica addition resulted in large increase in Blaines surface area of cement. The normal consistency of these blends was also higher. For samples containing 2-3 percent nanosilica, the increase in normal consistency (NC) was in the range of 7.14-15.33 percent of the NC of the control OPC. For samples containing 5 percent nanosilica, the increase in NC was much higher, in the range of 36.67-42.86 percent. The change in NC of samples containing microsilica was in the range of (-) 3.57-11.33 percent of the NC of control OPC. Samples containing nanosilica exhibited shorter setting times. The shortening of setting times is considered an indication of acceleration of rate of initial hydration reaction. The flexural strengths of all the OPC-1 blends containing nanosilica were higher compared to the control OPC-1. Higher contents of nanosilica, in general, led to higher flexural strengths. The increase in flexural strength over the period of 1 to 28 days, obtained with 2, 3 and 5 percent nanosilica was in the range of 6.25 -26.09, 12.5 -30.43 and 7.81 115 percent, respectively. The increase in flexural strengths over the period of 1 to 7 days was significantly higher compared to the increase obtained at 28 days. The flexural strengths of OPC-2 blends containing 2 and 3 percent nanosilica were generally same as that of control OPC-2. The flexural strengths of OPC-2 blends containing 5 percent nanosilica and 5 & 10 percent microsilica were generally lower than that of control OPC-2. The 28 day flexural strengths of all the blends were nearly same. OPC-2 had significantly higher alumina and lower silica content compared to OPC-1. The lime saturation factor and alumina modulus of OPC-1 and OPC-2 were 85.64 & 94.51 and 2.86 & 2.02 respectively. No clear trends in the compressive strengths of the blends, at same w/c ratio of 0.5, were observed with either OPC-1 or OPC-2. The OPC-1 blend containing 5 percent nanosilica had significantly higher strengths at the early ages of 1 and 3 days, the increase being 53.42 and 25.86 percent, respectively. For OPC-2 blend containing 5 percent nanosilica the strength increase was observed only at the age of 1 day, the increase being 24.24 percent. Any positive effects of nanosilica/ microsilica on compressive strengths of mortars of same consistency were apparently overshadowed by the higher w/c ratios used for achieving same consistency. As a result the compressive strengths of blends were generally lower than or comparable to compressive strengths of control OPC samples.

1.

INTRODUCTION

Investigations on elucidation of nanostructure and nano-modification of cement/ concrete, have been reported in recent scientific literature. A better understanding and ability to manipulate the nanostructure is considered important for achieving further improvement in the performance and durability characteristics of cementitious systems and achieve sustainable development. The performance of cements depends on nanoscale structure and properties of cement hydration products. Possible approaches for modifying the nanostructure of cementitious materials include incorporation of nano-sized particles of silica in cementitious matrix and is expected to improve the properties, such as packing density and early hydration rate, of cement mortar and concrete (1,2). The various factors contributing to the beneficial action of nano-particles on the microstructure and performance of cement-based materials include: filling of the voids between cement grains by nanoparticles; well-dispersed nano-particles acting as centers of crystallization of cement hydrates and thus accelerating the hydration; nano-particles favoring the formation of small-sized crystals (such as Ca(OH)2 and AFm) and small-sized uniform clusters of C-S-H and nano-SiO2 participating in the pozzolanic reactions resulting in the consumption of Ca(OH)2 and formation of extra C-S-H (3). Use of nanoscale pozzolans in cementitious formulations has been reported to result in not only higher early strength but also considerably higher final strength (4). The compressive strength of cement mortars with nano-SiO2 and microsilica at various water/ cementitious material ratios have been reported (5). The compressive strengths of mortars with nano-SiO2 particles were found to be higher than those of mortars containing silica fume at 7 and 28 days. Thus the nano-particles were found more effective in enhancing strength than silica fume. The results further indicated that nano-scale SiO2 behaved not only as a filler to improve microstructure, but also as an activator to promote pozzolanic reaction. The compressive and flexural strengths at 28 days, of the cement mortars containing nano-particles of SiO 2 or Fe2O3, have been reported to be higher compared to those of a plain cement mortar with the same water binder ratio (6). The SEM study of the microstructures of the cement mortar mixed with the nanoparticles and the plain cement mortar showed that the nano-Fe2O3 and nano-SiO2 filled up the pores and reduced Ca(OH)2 (7). Evaluation of the properties of high-volume fly ash high-strength concrete incorporating nano-SiO2 (SHFAC) has been reported (8). The results were compared with those of control Portland cement concrete (PCC) and of high-volume fly ash high-strength concrete (HFAC). Significant strength increases of SHFAC compared to the high-volume fly ash highstrength (HFAC) were observed as early as after 3 days curing, and improvements in the pore size distribution of SHFAC were also observed. In most of the above mentioned investigations, improvements in the properties of mortar/ concrete have been reported. In the present paper we report the results of our investigations on the effects of nanosilica powder dry blended with OPC, on the performance of OPC. 2. 2.1 EXPERIMENTAL Materials

Two samples of 43 Grade ordinary Portland cement (OPC), meeting the requirements of IS 8112:1989 (Indian Standard: Specification for 43 Grade Ordinary Portland cement) were procured from local market. Sample of nanosilica, having average particle size of 15 nm, was procured from M/s. MKnano (Division of M K Impex), Canada. The sample of microsilica was obtained from M/s. Elkem India (Pvt.) Ltd. The average particle size of microsilica was 295 nm.

2.2

Preparation of Blends of OPC and Nano/ Microsilica

Blends of OPC with 2, 3 & 5 percent nanosilica and 5 & 10 percent microsilica were prepared by substituting equal mass of OPC with nano/ microsilica. The blending operation was carried out in a batch type laboratory ball mill using 15-20 balls of 25-30 mm diameter and running the mill for a period of 30 minutes. Prior to feeding to ball mill, the nano/ microsilica was added to 0.5 kg of cement in a plastic container of 2 kg capacity and shaken vigorously for 10 minutes. This mixture along with the balance cement was blended in the ball mill. The size of each batch for ball mill blending was 6 kg. 2.2 Evaluation of Blends of OPC and Nano/ Microsilica

The blends containing nanosilica / microsilica as well as control OPC samples (OPC 1 and OPC 2) were evaluated for their Blaines fineness, normal consistency, specific gravity, setting time, flexural strength, and compressive strength as per the procedures specified in IS: 4031 - 1988 (Indian Standard: Methods of physical tests for hydraulic cement). The normal consistency was determined using a Vicat apparatus where the needle had been replaced with a plunger. The flexural strengths were determined using 1: 3 cement-sand mortar prisms of 40 x 40 x 160 mm. The mortars were prepared at a w/c ratio of 0.50 in a mechanical paddle type mixer following the procedure specified in IS 4031(part 8) 1988 (Indian Standard: Determination of transverse and compressive strength of plastic mortar using prism). The two halves of the prism obtained after the flexural strength testing were used for the determination of compressive strength. The compressive strengths of mortars of same consistency were determined on 70.6 mm cubes prepared using 1:3 cement sand mortars and computed water content following the procedure specified in IS 4031(part 6) 1988 (Indian Standard: Determination of compressive strength of hydraulic cement other than masonry cement). 3. 3.1 RESULTS AND DISCUSSION Materials

The chemical analyses of OPC, nanosilica and microsilica samples are given in Table 1. OPC-2 had significantly higher alumina and lower silica content compared to OPC-1. The lime saturation factor and alumina modulus of OPC-1 and OPC-2 were 85.64 & 94.51 and 2.86 & 2.02 respectively. The silica content of nanosilica and microsilica was 98.57 and 88.59 percent, respectively. Table 1 Chemical composition of OPC, nanosilica and microsilica samples Sl. No. 1 2 3 4 Sample Code OPC-1 OPC-2 NS-1 MS-1 LOI 3.14 1.86 CaO 61.05 61.86 SiO2 22.16 19.23 98.57 88.59 Al2O3 4.29 6.03 Fe2O3 3.45 3.47 MgO 2.57 2.39 SO3 2.26 2.86 Na2O 0.17 0.55 K2O 0.55 0.99 -

Table 2 Composition and physical properties of blends prepared with OPC 1 and nano/ microsilica

Code No.

Composition OPC-1 Nanosilica % 0 2 3 5 0 0

Physical Properties Initial Setting Time (Mts.) 167 74 55 15 200 210 Final Setting Time (Mts.) 302 224 150 50 240 275

Micro- Blaines, Normal Specific silica m2/Kg Consistency, Gravity % % 0 0 0 0 5 10 327.0 542.0 564.6 867.5 399.5 463.7 28.0 30.0 31.0 40.0 27.0 30.0 3.15 3.09 3.08 3.0 3.10 3.0

OPC-1 OPC-1A OPC-1B OPC-1C OPC-1D OPC-1E

100 98 97 95 95 90

Table 3 Composition and physical properties of blends prepared with OPC 2 and nano/ microsilica

Code No

Composition OPC-2 Nanosilica % 0 2 3 5 0 0 Microsilica % 0 0 0 0 5 10

Physical Properties Blaines, Normal Specific m2/Kg Consistency, Gravity % 268.2 476.5 540.2 839.0 322.0 470.0 30.0 33.0 34.6 41.0 32.4 33.4 3.14 3.11 3.10 3.05 3.05 3.05 Initial Setting Time (Mts.) 170 165 140 115 150 140 Final Setting Time (Mts.) 275 270 260 190 240 230

OPC-2 OPC-2A OPC-2B OPC-2C OPC-2D OPC-2E

100 98 97 95 95 90

3.2

Composition, fineness, specific gravity, normal consistency and setting time of cement blends

The composition, fineness, specific gravity, normal consistency and setting time of cement blends prepared using OPC 1 and OPC 2 are given in Table 2 and Table 3 respectively. Increasing content of nanosilica / microsilica resulted in higher values of Blaines fineness and lower values of specific gravity. In blends OPC 1A and OPC 2A, having 2 percent nanosilica replacing cement, the Blaines fineness increased from 327 to 542 m 2/Kg and from 268.2 to 476.5 m2/Kg, respectively. At five percent replacement of cement by nanosilica, the Blaines fineness of OPC 1C and OPC 2C was 867.5 and 839.0 m2/Kg, respectively. The increase in fineness affected by microsilica was much lower than those obtained with nanosilica. The normal consistency (NC) of blends containing 2-3 percent nanosilica was increased from 28 percent to 30 & 31 percent for OPC 1 blends and from 30 percent to 33 & 34.6 percent for OPC 2 blends. The percentage increase in NC of blends containing 2-3 percent nanosilica was in the range of 7.14-15.33 percent of the NC of the control OPC. For samples containing 5 percent nanosilica, the increase in NC was much higher, in the range of 36.67-42.86 percent. The change in NC of samples containing microsilica was in the range of (-)3.57-11.33 percent of the NC of control OPC. Samples containing nanosilica exhibited shorter setting times, though the extent by which the setting times were shortened were different for the two OPC samples. For OPC 1 nanosilica blends the initial and final setting times were in the range of 15-74 and 50-224 minutes, respectively, compared to 167 and 302 minutes for control sample, OPC-1. The percentage decrease in initial and final setting times of OPC 1 nanosilica blends were in the range of 55.6991.02 percent and 25.83-83.44 percent, respectively, compared to the initial and final setting times of control OPC. For OPC 2 nanosilica blends the initial and final setting times were shortened by 2.99-32.93 percent and 1.82-30.91 percent, respectively. The shortening of setting times is considered an indication of acceleration of early stage hydration reaction. Samples containing microsilica also showed shortened final setting times, the shortening being in the range of 8.9420.53 percent of the final setting time of control OPC. However, the initial setting times of OPC 1 microsilica blends were increased by 20-25 percent of the initial setting time of OPC-1. 3.3 Flexural strength of cement blends

The flexural strengths of all the OPC-1 blends containing nanosilica were higher compared to the control OPC-1 (Table 4). Higher contents of nanosilica, in general, led to higher flexural strengths. The increase in flexural strength over the period of 1 to 28 days, obtained with 2, 3 and 5 percent nanosilica was in the range of 6.25 -26.09, 12.5 -30.43 and 7.81 115 percent. The increase in flexural strengths over the period of 1 to 7 days was significantly higher compared to the increase obtained at 28 days. The flexural strengths of OPC-1 blends with microsilica were both higher as well as lower and did not show any clear trends when compared with the flexural strengths of control OPC-1. The relative flexural strengths of OPC-1 blends are shown in Figure 1A. At 28 days all the blends had nearly same strengths. At early ages nanosilica blends showed significantly higher strengths. The flexural strengths of OPC-2 blends with nano/ microsilica are given in Table 5. The flexural strengths of blends containing 2 and 3 percent nano/ microsilica were generally same as that of control OPC-2. The flexural strengths of blends containing 5 percent nanosilica and 5 & 10 percent microsilica were generally lower than that of control OPC (Figure 1B). The 28 day strengths of all the blends were nearly same.

Table 4 Flexural and compressive strengths of OPC-1 and nano/ microsilica blends at w/c ratio of 0.50 Code No. 1D OPC-1 OPC-1A OPC-1B OPC-1C OPC-1D OPC-1E 0.80 0.90 (12.5) 1.03 (28.75) 1.72 (115) 0.52 (-35.0) 0.64 (-20) Flexural Strength, MPa 3D 3.30 3.90 (18.18 ) 4.30 (30.30 ) 5.50 (66.67 ) 7D 28 D 6.40 6.80 (6.25) 7.20 (12.50) 6.90 (7.81) 6.40 (0) 6.81 (6.41) 1D 3.80 3.50 (-7.89) 4.90 (28.95) 5.83 (53.42) 4.00 (5.26) 2.28 (-40) Compressive strength , MPa 3D 11.60 13.20 (13.79) 10.50 (-9.48) 14.60 (25.86) 10.50 (-9.48) 7.37 (-36.47) 7D 15.40 16.00 (3.90) 13.60 (-11.69) 16.80 (9.09) 14.50 (-5.84) 11.30 (-26.62) 28 D 18.50 17.60 (-4.86) 24.90 (34.59) 19.60 (5.95) 17.00 (-8.11) 17.50 (-5.41)

4.60 5.80 (26.09 ) 6.00 (30.43 ) 6.70 (45.65 ) 5.50 3.50 (19.57 (6.06) ) 2.79 4.26 (-15.45) -7.39)

Note : Values within brackets are the percentage increase/ decrease over OPC -1

Table 5 Flexural and compressive strengths of OPC-2 and nano/ microsilica blends at w/c ratio of 0.50 Code No. OPC-2 OPC-2A OPC-2B OPC-2C OPC-2D OPC-2E Flexural Strength, MPa 1D 4.29 3D 6.58 7D 7.73 28 D 8.48 1D 13.2 11.0 (-16.67) 11.9 (-9.85) 16.4 (24.24) 10.1 (-23.48) 11.8 (-10.61) Compressive strength , MPa 3D 18.9 13.9 (-26.46) 16.5 (-12.70) 18.7 (-1.06) 12.3 (-34.92) 14.5 (-23.28) 7D 21.2 18.3 (-13.68) 19.7 (-7.08) 21.4 (0.94) 13.6 (-35.85) 18.8 (-11.32) 28 D 25.8 22.8 (-11.63) 23.8 (-7.75) 25.7 (-0.39) 19.9 (-22.87) 24.6 (-4.65)

4.29 6.19 7.58 8.58 (0) (-5.93) (-1.94) (1.18) 4.29 6.67 7.85 8.59 (0) (1.37) (1.55) (1.30) 4.79 5.90 6.62 8.05 (11.66) (-10.33) (-14.36) (-5.07) 3.86 4.95 5.69 7.44 (-10.02) (-24.77) (-26.39) (-12.26) 4.15 5.15 7.15 8.05 (-3.26) (-21.73) (-7.50) (-5.07)

Note : Values within brackets are the percentage increase/ decrease over OPC -2

250
E STRENGTH RELATIVE STRENGTH RELATIVE STRENGTH

OPC 1 Blends at same consistency

180

200
RELATIVE STRENGTH RELATIVE STRENGTH
28D

160 140 120

1D 3D 7D

OPC-1 OPC-1B OPC-1D

28D

1D 3D 7D Fig 1A: Relative flexural strength of OPC 1 Blends

150 180
160 100 140 120 50 100

Fig 1B: Relative flexural strength of OPC 2 Blends

100 180 80 160 60 140

1D 3D 7D

OPC-1 OPC-1B OPC-1D

28D

1D 3D 7D 28D Fig 1C: Relative compressive strength of OPC 1 Blends at W/C=0.5

180

Fig 1D: Relative compressive strength of OPC 2 Blends at W/C=0.5

120 40 100 20

0 80 160
60 140
1D

800 60 40 20

OPC-1 OPC-1B OPC-1D

Fig 1E: Relative compressive strength of

40 120 20 100

3D

7D

28D

0 80

180 160 RELATIVE STRENGTH 140

1D 3D 7D 28D

Fig 1F: Relative compressive strength of OPC 2 blends at same consistency

OPC-2 OPC-2B OPC-2D

120 100 80 60 40 20 0

3.4

Compressive Strength of cement blends at same w/c ratio

The compressive strengths of OPC-1 and OPC-2 blends with nano/ microsilica, determined on mortar prisms prepared using same w/c ratio of 0.5, are given in Tables 4 and 5 and their relative compressive strengths are given in Figures 1C and 1D. No clear trends in the compressive strengths of the blends were observed with either OPC-1 or OPC-2. The OPC-1 blend containing 5 percent nanosilica had significantly higher strengths at the early ages of 1 and 3 days, the increase being 53.42 and 25.86 percent, respectively (Figure). For OPC-2 blend containing 5 percent nanosilica the strength increase was observed only at the age of 1 day, the increase being 24.24 percent. The early strengths of blends containing microsilica were in general lower than those of control OPC samples.

3.5

Compressive Strength of cement blends at same consistency

The compressive strengths of OPC-1 and OPC-2 blends with nano/ microsilica, determined on 1: 3 cement sand mortar cubes using mortars of same consistency, are given in Tables 6 and 7 and their relative compressive strengths are given in Figures 1E and 1F. As the water content used for preparation of mortars was arrived at taking into consideration the normal consistency of cement blends (as per IS 4031 part 6), the w/c ratio was different for different blends. The increasing content of nano/ microsilica resulted in higher and higher w/c ratios being used for achieving same mortar consistency. The maximum increase in w/c ratio was affected by 5 percent nanosilica. Any positive effects of nanosilica/ microsilica on compressive strengths were apparently overshadowed by the higher w/c ratios with the result that the compressive strengths of blends were generally lower than or comparable to compressive strengths of control OPC samples. 3.6 Discussion

The blending of nanosilica/ microsilica powder to OPC resulted in significant increase in the surface area of cements. This led to significant increase in the normal consistency of cement blends. The increase in NC was much higher in blends containing 5 percent nanosilica. The blends containing nanosilica also showed shorter setting times. Shortening of setting times indicated acceleration of initial hydration reaction. This was in agreement with the reported accelerating effect of nanosilica on cement hydration reaction (3). The results obtained with OPC-1 indicated that at same w/c ratio the increase in flexural strength was higher for higher contents of nanosilica. Further, the increase in early flexural strength was substantially higher compared to increase at 28 days. This again emphasized the accelerating effect of nanosilica on cement hydration reaction. The substantial increase in normal consistency of blends containing 5 percent nanosilica indicated the need for using superplastizers at 5 percent or higher content of nanosilica. The results obtained with OPC-2 blends containing 2 & 3 percent nanosilica did not show any substantial increase in flexural strength and the blend containing 5 percent nanosilica showed lower strength. No clear trends in the compressive strengths of the blends, either at same w/c ratio or at same consistency, were observed with either OPC-1 or OPC-2. These results indicated the need to take up further work on evaluation of OPC-nanosilica blends, possibly using higher contents of nanosilica along with superplasticizers to control any abnormal rise in water requirement for maintaining same consistency

Table 6 Compressive strengths of OPC-1 and nano/ microsilica blends

at same consistency Code No. OPC-1 OPC-1A OPC-1B OPC-1C OPC-1D OPC-1E w/c ratio 0.40 0.42 0.43 0.52 0.39 0.42 Compressive strength, MPa 1D 11.00 10.20 (-7.27) 11.00 (0) 6.64 (-39.64) 12.00 (9.09) 6.76 (-38.55) 3D 25.80 27.70 (7.36) 27.00 (4.65) 19.51 (-24.38) 29.10 (12.79) 21.18 (-17.91) 7D 35.80 36.20 (1.12) 37.10 (3.63) 30.02 (-16.15) 38.10 (6.42) 29.30 (-18.16) 28 D 53.60 50.00 (-6.72) 53.00 (-1.12) 38.00 (-29.1) 52.00 (-2.99) 48.00 (-10.45)

Note : Values within brackets are the percentage increase/ decrease over OPC -1

Table 7 Compressive strengths of OPC-2 and nano/ microsilica blends at same consistency Compressive strength, MPa Code No. OPC-2 OPC-2A OPC-2B OPC-2C OPC-2D OPC-2E w/c ratio 0.42 0.45 0.47 0.53 0.44 0.45 1D 25.6 22.4 (-12.50) 23.0 (-10.16) 18.0 (-26.69) 17.2 (-32.81) 18.1 (-29.3) 3D 34.0 30.6 (-10.0) 29.5 (-13.24) 28.6 (-15.88) 29.0 (-14.71) 29.7 (-12.65) 7D 39.7 40.0 (0.76) 40.6 (2.27) 36.6 (-7.81) 31.0 (-21.91) 35.1 (-11.59) 28 D 48.2 46.0 (-4.56) 42.2 (-12.45) 40.5 (-15.98) 41.5 (-13.90) 51.2 (6.22)

Note : Values within brackets are the percentage increase/ decrease over OPC -2

4.0

CONCLUSIONS Nanosilica addition, in the range of 2-5 percent (replacing equal content of OPC), resulted in substantial increase in the Blaines fineness and normal consistency of cement blends. Presence of nanosilica resulted in shortening of setting times and indicated acceleratory effect of nanosilica on early cement hydration. Nanosilica addition, in some cases, resulted in higher flexural strengths especially at early ages. Further, higher content of nanosilica led to higher increases in flexural strength. No clear cut trends were observed in other cases, especially regarding compressive strengths of mortars.

i. ii.
iii. iv.

ACKNOWLEDGEMENT This paper is based on R & D studies carried out at National Council for Cement and Building Materials, New Delhi, India. This paper is published with the permission of the Director General of the Council.

REFERENCES

1.

Schmidt M., Stephan D., Krelaus R. And Geisenhansluke C. (2007), The promising dimension in building and construction: nanoparticles, nanoscopic structures and interface phenomena, Part 1, Cement International, 5 (4) , 86-100, 2007. Schmidt M., Stephan D., Krelaus R. And Geisenhansluke C. (2007), The promising dimension in building and construction: nanoparticles, nanoscopic structures and interface phenomena, Part 2, Cement International, 5 (6) , 72-85, 2007. Sobolev K. (2006), Nanomodification of cement, NSF Workshop on Nanomodification of Cementitious Materials: Portland Cement Concrete and Asphalt Concrete, August 8-11, 2006. Korpa A. and Trettin R, Nanaoscale pozzolans for improving ultra high performance cementitious binders, Cement International, 5 (1), 74-83, 2007. Jo B., Kim C., Tae G. and Park J., Characteristics of cement mortar with nano-SiO2 particles ACI Materials Journal, July-August 2007, 404-407. Li H. , Xiao H. and Ou J. (2004_II), A study on mechanical and pressure-sensitive properties of cement mortar with nanophase materials, Cement and Concrete Research, 34 (3), Pages 435-438, 2004. Li H. , Xiao H. Yuan J. and Ou J. (2004_II), Microstructure of cement mortar with nanoparticles, Composites Part B: Engineering, 35 (3), Pages 435-438, 2004.

2.

3.

4. 5. 6.

7.

28D 7D 1D 3D

8.

Li G. (2004), Properties of high-volume fly ash concrete incorporating nano-SiO2, Cement and Concrete Research, 34 (6), Pages 1043-1049, 2004.