Construction and Building

Construction and Building Materials 21 (2007) 539545

MATERIALS
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Inuence of nano-SiO2 addition on properties of hardened cement paste as compared with silica fume
Ye Qing
a

a,b,*

, Zhang Zenan c, Kong Deyu a, Chen Rongshen

College of Architecture and Civil Engineering, Zhejiang University of Technology, 310014 Hangzhou, PR China b Department of Civil Engineering, Quzhou College, 324006 Quzhou, PR China c Department of Physics, Zhejiang University of Technology, 310014 Hangzhou, PR China Received 4 March 2005; received in revised form 5 September 2005; accepted 7 September 2005 Available online 24 October 2005

Abstract The inuence of nano-SiO2 (NS) addition on properties of hardened cement paste (hcp) as compared with silica fume (SF) has been studied through measurement of compressive and bond strengths of hcp, and by XRD and SEM analysis. Results indicated that the inuence of NS and SF on consistency and setting time of fresh cement paste showed dierent. NS made cement paste thicker and NS accelerated the cement hydration process. Compressive strengths of hcp and bond strengths of pasteaggregate interface incorporating NS were obviously higher than those incorporating SF, especially at early ages. And with increasing the NS content, the rate of bond strength increase was more than that of their compressive strength increase. With 3% NS added, NS digested calcium hydroxide (CH) crystals, decreased the orientation of CH crystals, reduced the crystal size of CH gathered at the interface and improved the interface more eectively than SF. The results suggest that with a small amount of added NS, the CH crystals at the interface between hcp and aggregate at early ages may be eectively absorbed in high performance concrete (HPC). 2005 Elsevier Ltd. All rights reserved.
Keywords: Hardened cement paste; Interface; Nano-SiO2; Mechanical property; Silica fume

1. Introduction In this new century, the technology of nano-structured material is developing at an astonishing speed and will be applied extensively with many materials. Although cement is a common building material, its main hydrate CSH gel is a natural nano-structured material [15]. The durability and mechanical properties of HPC are mainly dependent on the gradually rening structure of hcp and the gradually improving pasteaggregate interface incorporating additions and admixtures. Many researchers have applied slag, y-ash and silica fume (SF) to improving cement-based materials, and have achieved great successes, such as HPC and reactive powder concrete and so on. SF
Corresponding author. Tel.: +86 571 85816061; fax: +86 571 88320124. E-mail address: zjutyeqing@163.com (Q. Ye). 0950-0618/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2005.09.001
*

belongs to the category of highly pozzolanic materials because it consists essentially of silica in non-crystalline form with a high specic surface, and thus exhibits great pozzolanic activity. But the activity of SF at early ages is low according to the literature [69]. Mitchell et al. [6] reported that the XRD pattern of SF, put into saturated calcium hydroxide (CH) solution, changed little up to 7 days and extensive CSH formation had occurred after 120 days. Li et al. [9] showed that only 75% of SF was consumed in a cement paste after 90 days of hydration. The aggregatepaste interface is regarded as the most sensitive area within the structure of concrete, where a number of defects exist and the concrete failure process commences easily. Through SEM and XRD examinations of the interfacial transition zone in pastes cast against glass slides, Barnes et al. [10] and Grandet and Ollivier [11] reported the occurrence of duplex lms, comprising a layer of CH crystals in contact with the glass and oriented with

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their c-axes normal to its surface, and a layer of CSH further out into the paste. With additions of pozzolanic materials such as slag, y-ash and silica fume added, the interface structure has been improved, especially in HPC [1215]. In this paper, using the experience of nano-technology in ceramics and polymer for reference, the inuence of NS on properties of hcp was studied as compared with silica fume, in order to improve the microstructure of hcp, thus to enhance the durability and mechanical properties of cement-based materials. Furthermore, for HPC containing SF or y-ash or slag, with the addition of 13% NS, we hope to produce a new high performance concrete with much better properties. 2. Experimental procedure 2.1. Raw materials A commercial Chinese ordinary Portland cement (C) (42.5 grade, Blaine specic surface 310 m2/kg) complying with Chinese standard (GB 175) was used. Its composition (wt%) is 81% clinker, 13% slag and 6% gypsum, and the Bogue composition of the clinker is 56% C3S, 18% C2S, 8% C3A and 12% C4AF. Both NS and SF in this study were commercially available undensied materials, supplied by Mingri Nano-material Ltd. and Zhunyi Ferroalloy Ltd. in China, respectively. A superplasticizer (SM) used was a commercial sulphonated melamine formaldehyde polymer (liquid solution, water content 70%) with special gravity 1.2 g/cm3 and water reduction up to 20%. Tap water (W) was used in all experiments. Chemical compositions and physical properties of clinker, slag, gypsum, SF and NS are shown in Table 1. 2.2. Experimental programs (1) Preparation of paste specimen. Cement pastes incorporating NS or SF were prepared at (near) standard consistency using a planetary mixer (ISO). For all the pastes, a cement plus addition:water:superplasticizer ratio of 1:0.22:0.025 was used, as shown in Table 2. Cement with NS or SF was fully mixed under the condition of dry process beforehand. The mixing consists of a sequence of mixings that involve a total of

2.0 min at a paddle speed of both 62 rpm (revolution) and 140 rpm (rotation), a 15 s stop and a total of 2.0 min at a speed of both 125 rpm (revolution) and 285 rpm (rotation). (2) Test of consistency and setting time of fresh pastes. The consistency and the setting time of fresh pastes were tested according to ISO 9597:1989. The consistency was ascertained by putting the paste in a mould consisting of a steel ring (40 mm in height) on a sheet of glass and by determining the penetration depth of a plunger applied to the top surface of the paste specimen. The initial and the nal setting time were determined with the needle of the Vicat apparatus. (3) Test of paste compressive strength. The fresh paste was cast into cubic molds (25 25 25 mm) to prepare specimens on a vibrating table for a measurement of compressive strength. Three cubes were tested for each sample at the given age, by a hydraulic press with 100 kN capacity and 0.5 MPa/s loading speed. Each strength value was an average of three specimens. (4) Test of bond strength of pasteaggregate interface (or paste exural strength set with glass plate). The fresh paste was cast into square-bar moulds 40 40 160 mm on a vibrating table, and then a glass plate (39.8 39.8 3 mm) was set into the middle of the square-bar specimen with the plate parallel to the bar cross-section. With ISO method for cement exural strength test for reference, three specimens were tested for each sample at the given age. The span for exural strength test and the compressed area for compressive strength are 100 and 40 40 mm, respectively. Namely, the bond strength is represented by exural strength. (5) Preparation of pasteaggregate interface specimen for microstructure analysis. At rst, glass plate (19.8 19.8 3 mm) was prepared, and the plate was set into the bottom of cubic mold (20 20 20 mm). Then the fresh paste was cast into the cubic molds on a vibrating table. (6) Microstructure analysis at interface. At the given age, when glass plate was split apart between hcp and glass, the fracture surface (interface) on hcp was analysed by XRD and SEM immediately, in order to determine the degree of interaction between CH and

Table 1 Chemical compositions and physical properties of clinker, slag, gypsum, silica fume and nano-SiO2 Chemical composition (wt%) SiO2 Clinker Slag Gypsum SF NS 21.05 31.55 4.96 92.10 99.90 Al2O3 5.56 13.95 0.46 2.04 Fe2O3 4.03 1.08 0.26 1.08 CaO 64.27 41.42 29.61 0.45 MgO 1.02 8.20 1.45 0.58 SO3 0.75 37.56 0.44 Physical properties Average of diameter (nm) Specic surface (m2/g) Density (g/cm3) Loose density (g/cm3)

180 15

21.5 160

2.22 2.12

0.21 0.15

Q. Ye et al. / Construction and Building Materials 21 (2007) 539545 Table 2 Mix proportions, compressive and bond strengths of pastes made out of cement and NS or SF Sample Mix proportion in mass C CO A1 A2 A3 A5 B2 B3 B5
a

541

Consistencya (mm)

Setting time Initial Final 4h23m 4h05m 3h50m 3h40m 3h06m 4h45m 5h20m 5h28m Dt 1h26m 1h08m 0h55m 0h52m 0h50m 0h55m 0h45m 0h43m

Compressive strength (MPa) (%) 1d 48.9 49.2 49.8 52.0 53.0 47.5 47.3 47.0 (100) (101) (102) (106) (108) (97) (97) (96) 3d 61.1 71.6 72.6 82.2 86.1 61.0 60.4 60.0 (100) (117) (119) (135) (141) (100) (99) (98) 28d 79.2 94.7 95.8 97.6 98.8 84.2 92.0 95.3 (100) (120) (121) (123) (125) (106) (116) (120) 60d 94.9 101.6 102.5 105.8 108.8 101.5 104.3 106.9 (100) (107) (108) (111) (115) (107) (110) (113)

Bond strength (MPa) (%) 7d 5.1 5.9 6.2 6.6 7.3 5.2 5.0 4.9 (100) (116) (122) (129) (143) (102) (98) (96) 28d 5.8 7.3 8.3 10.0 10.9 6.3 6.7 7.1 (100) (126) (143) (172) (188) (109) (116) (122)

NS 0 1 2 3 5 0 0 0

SF 0 0 0 0 0 2 3 5

W 22 22 22 22 22 22 22 22

SM 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 34 34 33 33 32 35 35 36

100 99 98 97 95 98 97 95

2h57m 2h57m 2h55m 2h48m 2h16m 3h50m 4h35m 4h45m

Penetration depth.

NS or SF, and to observe the orientation, size and morphology of CH crystals or other hydration products at the interface. (7) Curing conditions for specimens. All paste specimens, which were cured at (20 2) C and above 90% r.h. moisture, were demolded after 24 h, and then stored in water at (20 1) C. The above consistency, setting time, compressive and bond strength tests were repeated three times. 2.3. Equipment and test conditions X-ray diraction analyzer used is Rigaku D/Max-3B type with the following conditions: Cu Ka radiation, tube electric current 40 mA and tube voltage 40 kV, and scanning speed 1/min. Scanning electron microscope used is Hitachi S570 type. 3. Results 3.1. Degree of crystallinity of NS and SF Fig. 1 shows XRD powder patterns of NS and SF. Strong broad peaks of NS and SF were centered on 23 and 22 (2h), respectively, which was in keeping with the strong broad peak of a characteristic of amorphous SiO2. The results show that both NS and SF are in an amorphous state. 3.2. Consistency and setting time of fresh pastes The inuence of NS or SF addition on consistency and setting time of fresh pastes is presented in Table 2. With increasing the NS content, fresh pastes for sample A-series grew thicker gradually and their penetration depths (consistency value) decreased gently as compared with that of control sample CO. While with increasing the SF content, the pastes for sample B-series grew thinner and their depths increased. The setting of fresh pastes (sample A-series) was slightly accelerated but the dierence between the initial and the nal time decreased with increasing the NS content. While the setting of fresh pastes (sample B-series) was obviously retarded and the dierence was also de-

creased with increasing the SF content. The results indicate that the inuence of both NS and SF on consistency and setting shows dierent, and NS makes cement paste thicker and accelerates the cement setting process as compared with SF. 3.3. Compressive strength of pastes Table 2 also gives the variation of the compressive strength development of hcp with NS or SF added. It is found that all paste strengths of sample A-series were obviously higher than those of control sample CO especially at 3 days. Furthermore, with increasing the NS content, paste strengths increased. For example, compared with sample CO, the strengths of sample A3 increased by 6%, 35%, 23% and 11% at ages of 1 day, 3 days, 28 days and 60 days, respectively. However, with increasing the SF content, all paste strengths of sample B-series were slightly lower than those of sample CO at ages of 1 day and 3 days. But at ages of 28 days and 60 days, strengths with increasing the SF content were obviously higher than those of sample CO, and the strengths were slightly lower than those of sample A-series with the same content of addition. For example, as compared with sample CO, the strengths of sample B3 decreased by 3% and 1% at ages of 1 day and 3 days, and increased by 16% and 10% at ages of 28 days and 60 days, respectively. These results show that the compressive strength of hcp is enhanced with NS addition added, especially at early ages, and the pozzolanic activity of NS is much greater than that of SF.

Fig. 1. XRD powder pattern of nano-SiO2 and silica fume.

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3.4. Bond strength of pasteaggregate interface The variation of bond strength of pasteaggregate interface made from cement and NS or SF with time is shown in Table 2. Similarly to the compressive strengths, all bond strengths of sample A-series were obviously higher than those of control sample CO and than those of sample B-series. Moreover, with increasing the NS content, the rate of bond strength increase was more than that of their compressive strength increase. At the ages of 7 and 28 days bond strengths of sample A3 were, respectively, 6.6 and 10.0 MPa and were, respectively, 29% and 72% higher than that of sample CO, and were, respectively, 32% and 49% higher than that of sample B3. The results show that the bond strength at the interface between aggregate and hcp incorporating NS increases obviously and NS addition can improve the interface structure more eectively than SF. 3.5. Consumption of CH crystals gathered at the paste aggregate interface Fig. 2 shows the variation of interaction between CH and NS or SF at the interface with time determined by XRD pattern. The consumption of CH (crystals) content at the interface between glass plate and paste containing NS or SF can be demonstrated approximately by intensity changes of main diraction peaks of CH crystals, such as (0 0 1) crystal face, as well as (1 0 0) and (1 0 1) crystal faces (d = 0.490, 0.310 and 0.263 nm, respectively), neglecting the eect of orientation on the intensity. At the same ages, diraction peak intensities of (1 0 0) and (1 0 1) crystal faces of CH at the interface of sample A3 were almost equal to those of sample CO, but the intensity of (0 0 1) crystal face was much less than that of sample CO. For example, as compared with sample CO, the intensities of (0 0 1) crystal face at the interface of sample A3 decreased by 67%, 61% and 64% at ages of 1 day, 7 days and 28 days, respectively. Similarly to sample A3, intensities of (1 0 0) and (1 0 1) crystal faces of CH at the interface of sample B3 were almost equal to those of sample CO, but the intensity of (0 0 1) crystal face was less than that of sample CO. For instance, as compared with sample CO, the intensities of sample B3 decreased by 29%, 19% and 12%, respectively, at the same above ages. The results indicate that NS can consume more CH crystals at the interface and can improve the interface structure more eectively than SF. 3.6. CH orientation at the pasteaggregate interface The inuence of NS or SF on CH orientation at the pasteaggregate interface can be determined by XRD pattern as shown in Fig. 2. The orientation in this paper is dened as R = 1.35I(0 0 1)/I(1 0 1), where I(0 0 1) and I(1 0 1) is (0 0 1) and (1 0 1) crystal face peak intensity, respectively, and R is orientation index. At the interface between paste
Fig. 2. Variation of interaction between nano-SiO2 and Ca(OH)2 at the interface between paste and aggregate with time determined by XRD as compared with silica fume.

and glass plate, orientation indexes of control sample CO were very great and were 3.9, 3.6 and 3.6 at ages of 1 day, 7 days and 28 days, respectively, and the indexes of sample B3 were 3.4, 3.1 and 3.3. But those of sample A3

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were very small and were just 1.8, 1.6 and 1.5 at the same above ages. The results reveal that NS can decrease the orientation of CH crystals more eectively than SF. 3.7. CH micrographs at the pasteaggregate interface The variation of SEM micrographs of CH crystals gathered at the pasteaggregate interface with NS and SF added is presented in Fig. 3. Fig. 3(a) shows that, for sample CO, hexagonal plates of CH crystals occurred with their c-axes perpendicular to the glass surface. Edges of hexagonal plates were clear and the size of the biggest crystal CH was up to 10 lm in the SEM micrograph. CH micrographs at the interface of sample A3 are shown in Fig. 3(b). It can be seen that the big CH plates occurred with their c-axes also normal to the glass surface. But edges of hexagonal plates with eroded phenomenon were unclear, and the size of the biggest crystal CH was up to 4 lm in the SEM micrographs.

As shown in Fig. 3(c), for sample B3, CH plates also occurred with their c-axes perpendicular to the glass surface. Edges of hexagonal plates were clear similarly to sample CO and the size of the biggest crystal CH reached 7 lm. The results show that NS can reduce the size of CH crystals at the interface more eectively than SF. 4. Discussion It is common knowledge that SF has a high pozzolanic activity and is normally considered as the best mineral addition used for concrete up to now. When SF is added to cement or concrete, it acts both as a chemical inert ller, improving the physical structure and providing nucleation sites for hydration products, and as a pozzolan, reacting chemically with CH formed during hydration of cement, which will probably improve the pasteaggregate bond [15,16]. However, the pozzolanic activity of SF at early ages is low according to the aforementioned literature

Fig. 3. SEM micrographs of Ca(OH)2 crystals at the interface between aggregate and paste made from cement and nano-SiO2 at 28 days: (a) without NS; (b) with 3% NS; (c) with 3% SF.

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[811,16]. It is reported that the pozzolanic reaction between SF and CH formed during cement hydration begins to occur after 3 days of hydration. With ultrane particle size reducing to nano-structured one, such as SF particle size to that of NS, specic surface and the number of atoms in the surface increase rapidly. Owing to atoms in surface of nano-meter particles not being full of other coordinate atoms, there exit a lot of free bonds and unsaturated bonds or residual valence forces in the surface which lead the particles to be unstable state of thermodynamics. On the other hand, with the particle size reducing, there exit many uneven atom steps which increase chemical reaction area [17]. For this reason, the nano-meter particles, such as NS, have high surface energy; and atoms in the surface have a high activity, which leads the atoms to react on outer ones easily. Consequently, the pozzolanic activity of NS at early ages is higher than that of SF. The mechanisms that addition of NS has dierent effects on the properties of the cement paste, as compared with addition of SF, can be illustrated as follows. When a material with high specic surface is added to cement or concrete, it acts as the micro-ller of the cement particles, which can reduce the amount of water that lled in the void of the blending materials. However, replacing cement with a high specic surface material would increase the wettable surface area and the amount of water adsorbed. Thus, the nal water requirement will depend on which of the two above-mentioned factors will be superior. With replacement of less than 5% in this paper, the former factor may be superior for SF. But the later factor may be superior for NS, due to the very high specic surface area of the nano-meter sized particles, which would increase greatly the wettable surface area and the amount of water adsorbed. Thus addition of NS can make cement paste thicker. Because the specic surface of NS with 160 m2/g is much greater than that of SF with 21.5 m2/g, the reaction between SiO2 and Ca(OH)2 shows dierences between the cement paste incorporating NS and that incorporating SF. For NS having many unsaturated bonds SiO and Si in the surface, the reaction process between SiO2 and Ca(OH)2 may be as follows: BSiO HOH ! BSiOH react quickly BSi OH ! BSiOH react quickly BSiOH CaOH2 ! CSH 1 2 3

1) for NS [17]. So, NS can accelerate the cement setting process and the hydration process. It is the surface eects of nano-structured particles that cause the superiorities of cement paste incorporating NS to that incorporating SF. For this reason, NS can provide much more nucleation sites for hydration products than SF at early ages, and NS has a higher pozzolanic activity than SF. Therefore, incorporating NS can increase compressive strengths of hcp and bond strengths of paste aggregate interface, especially at early ages, and can improve the interface structure more eectively than incorporating SF. So, using a small amount of NS can enhance the durability and the mechanical properties of cementbased materials. 5. Conclusions The following conclusions may be drawn from the obtained experimental data: (1) Both nano-SiO2 and silica fume are in the amorphous state. (2) The inuence of nano-SiO2 and silica fume on consistency and setting time are dierent. Nano-SiO2 makes cement paste thicker and accelerates the cement hydration process. (3) Compressive strengths of hcp increase with increasing the nano-SiO2 content, especially at early ages. However the strengths of hcp decrease slightly with increasing the silica fume content at early ages, but increase at later ages. (4) Bond strengths of pasteaggregate interface incorporating NS are higher than those of control sample CO and than those incorporating SF. With increasing the NS content, the rate of bond strength increase is more than that of their compressive strength increase. (5) The pozzolanic activity of nano-SiO2 is much greater than that of silica fume. Nano-SiO2 consumes CH crystals, decreases the orientation of CH crystals, reduces the size of CH crystals at the interface and improves the interface structure more eectively than silica fume.

Acknowledgements The authors wish to thank the Center of Science Research, Zhejiang University of Technology of China for nancial support. References
[1] Taylor HFW. Nanostructure of CSH: current status. Adv Cem Bas Mater 1993;1:3846. [2] Richardson IG. The nature of the hydration products in hardened cement paste. Cem Concr Compos 2000;22:97113. [3] Zhang XZ. Nanostructure of calcium silicate hydrate gels in cement paste. J Am Ceram Soc 2000;83(10):26004.

For SF having many saturated bonds SiOSi and a little unsaturated bonds in the surface, the process may be as follows: BSiOSiB HOH ! BSiOH react slowly BSiOH CaOH2 ! CSH 4 5

In the cementwater system, the bond SiO of SF is not easy to break down owing to its higher bond energy. The rst step reaction (Eq. 4) for SF is slower than that (Eq.

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