Materials Science and Engineering A 424 (2006) 266274

Effect of nanosilica on characterization of Portland cement composite

Jeng-Ywan Shih, Ta-Peng Chang , Tien-Chin Hsiao
Department of Construction Engineering, National Taiwan University of Science and Technology, Taipei 10672, Taiwan, ROC Received 16 November 2005; accepted 4 March 2006

Abstract Both the lling effect and the pozzolanic reaction make siliceous materials as one of major ingredients of high-performance Portland cementbased composites. Hence, the introduction of nanosilica with ner particle size and larger silicon dioxide to the composite becomes a great deal of interest in recent years. In this study, a liquid-form of nanosilica particle with a spherical diameter of about 20 nm was incorporated into the Portland cement paste at ve different dosages and analyzed at four different ages to identify the nanosizing effects on the microstructures and material properties of composite cement paste. Experimental results show that the Portland cement composite with 0.60% of added nanosilica by weight of cement has an optimum compressive strength, in which the increase of compressive strength is about 43.8%. Moreover, the corresponding nanosilica paste of one portion of water mixed with nanosilica of 1.08 wt.% of water has the maximum absolute value of zeta potential of 41.3 mV. Properties through the analyses of NMR, BET and MIP also indicate that the microstructure of Portland cement composite with nanosilica evidently has a more solid, dense and stable bonding framework. 2006 Elsevier B.V. All rights reserved.
Keywords: Nanosilica; Cement paste; Compressive strength; Zeta potential

1. Introduction Due to results of the lling effect to reduce porosity by uniform distribution of particle size and the pozzolanic reaction that consumes calcium hydroxides (Ca(OH2 )) to yield calcium silicate hydrates (CSH), the silica fume, a conventional supplementary cementitious material, is one of the very important admixtures for producing the high-performance Portland cement-based concrete with enhancing strength and abrasion resistance along with reducing permeability and dry shrinkage [14]. In order to obtain further improvements of Portland cement-based composite (or alternatively called as cement composite for simplicity when appropriate hereinafter), siliceous materials of higher purity and ner size are introduced. In the past decade, novel properties of nanoparticles with 1100 nm scale have attracted enormous attention [5]. Among these nanoparticles, nanosilica is commonly used for reinforcement of polymer to increase the hardness, modulus, weatherability, ammability, and so on [610]. Likewise, some efforts on excellent mechanical properties and microstructure of cement composites with nanosilica have been also reported [11,12], in

Corresponding author. Tel.: +886 2 2737 6577; fax: +886 2 2737 6606. E-mail address: tpchang@mail.ntust.edu.tw (T.-P. Chang).

which a water reducing agent was always applied to aid the dispersion of nanosilica during the process of specimen preparation. Although, the water reducing agent may help improve the material properties of cement composites, some unpredicted interaction among water, water reducing agent, nanosilica and cement is anticipated to complicate the study on the chemical mechanism of such composite material. For this reason, in order to alleviate the complex interaction of state variables and to properly evaluate the inuencing effects of nanosilica on cement composites, this study does not include water reducing agent as one of the ingredients. Rather, only the addition of nanosilica in liquid form was included to investigate the characteristics of corresponding cement composite. On the other hand, the zeta potential is the electric potential around the particle on the slip surface within an electric double layer formed at the particleliquid interface. In the slip surface, the double layer is divided into two parts: the inner region named stern layer and the outer region called diffusive layer. Because the zeta potential performs the quantitative measure on the effective charge of particles, it is related to the stability and agglomeration processes. In other words, if the repulsive force between approaching particles becomes high enough, then they will repel each other to make them separable. On the contrary if the repulsive force is sufciently weak, then the particles will get together and ambient particles may also be seized in the growing

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.03.010

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agglomeration. So, when the absolute value of the zeta potential gets over a specic electric charge, the system will keep in a dispersing state. Therefore, when silica particles in the fresh Portland cement paste are under such spreading condition, the opportunity of producing calcium silicate hydrates, which plays a vital role of strength development, can rise apparently. In addition to using the compressive strength and zeta potential as two major indices to evaluate the effects of added nanosilica on the features of cement composite, other material properties such as degree of hydration, bonding pattern, and fractal dimension are also addressed. 2. Experimental program 2.1. Experimental techniques and facilities for microstructural properties The examination of microstructural properties of cement composite and nanosilica was conducted by one or more of the following methods and corresponding facilities, whichever suits the requirements: (1) Zeta potential measured by electrophoresis apparatus using Malvern Instruments Zetasizer 2000. (2) Degree of hydration assessed by nuclear magnetic resonance (NMR) using a Varian 400 MHz (one-pulse pattern, pulse delay 180 s.). (3) Specic surface measured by nitrogen adsorption according to the Brunauer, Emmett, and Teller (BET) method using a Micromeritics ASAP 200C. (4) Porosity analyzed by Mercury Intrusion Porosimeter (MIP) using a Micromeritics AutoPore IV 9520 (from atmospheric pressure to 414 MPa). 2.2. Materials Three major ingredients of cement composite were used in this study: (1) Type I Portland cement complying with ASTM C150 standard; (2) ordinary distilled water and (3) nanosilica (NS) in liquid form used as the admixture. The chemical compositions and physical properties of ASTM Type I Portland cement are given in Table 1. Basic material properties of nanosilica are given in Table 2. 2.3. Experimental variables, procedure and specimen preparation At the beginning, ve different water/cement (W/C) ratios of 0.25, 0.35, 0.45, 0.55 and 0.65 were used to mix the cement composite whose performance was carefully examined accordingly. Finally, the optimum water/cement (W/C) ratio was xed at 0.55. Five different dosages of nanosilica, 0.0, 0.2, 0.4, 0.6 and 0.8 wt.% of cement were added to the Portland cement paste to cast the specimens of cement composite. The mix proportions of these ve cement composites are given in Table 3. Cylindrical nanocomposite specimens of 25 mm 50 mm were used for the compressive test. Each experiment was per-

Table 1 Chemical compositions and physical properties of Type I Portland cement used in this study Chemical composition (mass%) SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 Free CaO LOI Physical properties Fineness (m2/kg) Specic weight Initial setting (min) Final setting (min) 20.31 5.05 3.16 62.43 3.81 2.48 0.4-78 1.49 349.0 3.15 185.0 292.0

Table 2 Basic material properties of nanosilica (NS) (in liquid form) Composition (mass%) Dimension pH value SiO2 (40.6%), H2 O (58.8%), others (0.6%) 20 nm (spherical shape) 10.1

formed at four ages of 7, 14, 28 and 56 days using three specimens prepared from same batch of mixture. All the specimens of cement composite were demoulded 24 h after they were cast and then immersed in the saturated limewater basin until 1 day before the test and then cured in the ambient temperature for 24 h. The test of compressive strength of cylindrical nanocomposite specimen was performed by a 10 tonnes material testing machine following the procedure of ASTM C39 standard. The zeta potential can be calculated from the velocity per unit electrical eld strength, which is the electrophoretic mobility. Thus the specimen used in the zeta potential test is in the form of a dilute suspension. The procedures of suspension preparation and zeta potential measurement are briey described as follows. After entering into deionized water, nanosilica was ultrasonically dispersed for 180 s in the solution to obtain the aqueous suspension. Then, the sample suspension was injected into the electrophoresis apparatus to determine the zeta potential of nanosilica. The average was decided as the experimental consequence by measuring the same suspension for ve times. Thus, the zeta potential tests of four various added dosages of nanosilica, 0.36, 0.72, 1.08, and 1.44 wt.% of water, in which these four mix proportions were corresponding to the mix tags of C-02, C-04, C-06 and C-08 of cement composite, were also
Table 3 Mix proportion of Portland cement composite Designation C-00 C-02 C-04 C-06 C-08 Cement:water:NS (by mass) 1:0.55:0.000 1:0.55:0.002 1:0.55:0.004 1:0.55:0.006 1:0.55:0.008

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investigated to gain the optimal addition. Finally, the test results of compressive strengths and zeta potentials were used as two performance indices to select the optimal nanocomposite from which its microstructural properties were examined. For the MIP analysis, the cylindrical disk specimens of 20 mm 10 mm were dried in an oven at 105 C for 24 h to reach a constant weight, and then were loaded into a penetrometer. After specimen was installed and evacuated to the required vacuum level, the penetrometer was backlled with mercury. As the pressure was increasing, the mercury was gradually entering the pores of specimens. Thus the volume of mercury deducted in the penetrometer is related to the volume of the pores lled. Hence, the volume of mercury penetrating into the pores can be obtained from the applied pressure from which the pore size distribution and pore volume of specimen can also estimated. 3. Results and discussion 3.1. Compressive strengths All the test data of compressive strengths of cement composite with ve dosages of NS at four ages are given in Fig. 1. Fig. 1 shows the development of mean values of compressive strength of test data with corresponding errors bars at four ages versus ve different added percentages of NS represented by ve vertical lines. Basically, the compressive strength at four ages increases with the increase of the amount of NS until it reaches an optimal amount of 0.6% and then drops to some lower values at 0.8% addition. The curve line of C-06 with the addition of NS of 0.6% shows the highest compressive strengths among all ages with the highest value of 65.62 MPa at age of 56 days. At least two likely mechanisms can be deduced to contribute to the increase of compressive strengths of hardened cement paste due to the addition of NS. The rst strengthening mechanism is the packing effect of small NS acted as ller

to ll into the interstitial spaces inside the skeleton of hardened microstructure of cement paste to increase its density as well as the strength. The second strengthening mechanism is the pozzolanic effect that combines glass-like silicon elements in NS with the lime elements of calcium oxide and hydroxide in cement to add the bonding strength and solid volume, resulting in higher compressive strength of hardened cement paste. Most pozzolanic reaction between the calcium hydroxide and amorphous silica (silicon dioxide) normally reacts slowly during a prolonged period of moist curing. Since the spherical particles of NS have an average particle diameter of about 20 nm which is about 1000-times ner than average cement particle of 20 m resulting in an extremely large surface area, the NS reacts very rapidly with the calcium hydroxide to form calcium silicate in an alkaline environment such as the pore solution of fresh Portland cement paste. For this reason, the contribution of added NS to the increase of strength of hardened cement paste becomes apparent as early as 14 days after hydration. These strengthening mechanisms of cement paste attributed to the addition of NS will be justied by the following microstructural examination in the following sections. 3.2. Zeta potentials The interactions between the NS particles with Portland cement are assessed using the Zeta potential measurements in a rheological state to determine the mechanism of dispersion. The zeta potential is the electro kinetic potential of a particle in an aqueous solution as determined by its electrophoretic mobility between particle and solution in an electric eld. By measuring the charge density of particles on a surface, the zeta potential is the electric magnitude of the repulsion or attraction between colloidal particles. Thus, the zeta potential is a major inuential parameter to study the dispersion mechanism of NS particles in an alkaline solution of Portland cement paste. Since the zeta potential of a particle is an indication of its electrostatic surface charge, usually, the zeta potential is expressed in the level of energy barrier preventing the proximity of particles [12]. Each particle has a natural electrostatic surface charge at different pH values of the ambient environment. When the values of pH of the environment vary from 2 to 12, zeta potentials will change from positive at low pH to negative at high pH. The isoelectric point (IEP) of each particle indicates the pH at which the natural surface charge is zero. Therefore, to enhance the dispersion behavior, the higher the absolute value of zeta potential is; the better the dispersion of particles will be. The ranges of IEPs of SiO2 are between pHs 2.0 and 2.5 [13]. If the pH value exceeds the corresponding pH value of IEP, the process of reaction takes place through Eq. (1) [14]. Hence, the zeta potential becomes negative because Si(O ) forms at the surface of SiO2 : Si(OH) + OH Si(O ) + H2 O (1)

Fig. 1. Compressive strengths of Portland cement composite at various additions of NS and ages.

The ratios of weights between NS and water (NS/water) for four mix proportions of C-02, C-04, C-06 and C-08 in Table 3 can be calculated as 0.36, 0.72, 1.08 and 1.44%, respectively. The zeta potentials for each mix proportion were measured ve

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3.3. Microstructural examination on performance of nanosilica in cement composite To justify the optimum macro-behavior of strengthen mechanism of hardened cement composite in terms of compressive strengths due to the addition of NS with an optimum added amount of 0.6 wt.% of cement, several microstructural examinations such as NMR, BET and MIP were also conducted in this study. For the purpose of comparison, both the specimens of harden cement composite with 0.6% addition of NS and without addition of NS at age of 56 days were used. 3.3.1. NMR examination The non-destructive and non-invasive measurement of nuclear magnetic resonance (NMR) measured on 29 Si nuclei has been used to study the behaviors of Portland cement powder, pure hardened Portland cement paste and hardened Portland cement composite with addition of 0.6% of NS. In a 29 Si NMR spectroscopy, the quantity of chemical shift of a nucleus, normally expressed in ppm, is the difference between the resonance frequency of the nucleus and the standard of tetramethylsilane, Si(CH3 )4 , abbreviated TMS. Let Qn represent a SiO4 tetrahedron with n bridging oxygens. The intensities of ve separate peaks appear around 70, 80, 88, 98 and 110 ppm in the NMR curve, denoted as Q0 , Q1 , Q2 , Q3 and Q4 , can be used as a base to characterize quantitatively the degree of hydration of tested sample through the curve given either by Lorentzian function or Gaussian function to t the experimental data of NMR curve [15]. All the test results of NMR experiments are shown in Figs. 4 and 5a and b, respectively. Fig. 4 is the NMR curve for pure Portland cement that only has a single peak of Q0 . Both Fig. 5a (hardened pure cement paste) and b (hardened cement composite with NS) show one sharp peak of Q0 and another wider peak containing both Q1 and Q2 . These two gures do not have either Q3 peak or Q4 peak. After some preliminary assessment on the suitability of the tted equation to t the experimental data, the Lorentzian func-

Fig. 2. Zeta potential by various additions.

times and the test results of each individual data and average value are presented in Fig. 2. As described in Section 3.1, the mix proportion of C-06 has the highest compressive strengths among all ages. The experimental data of zeta potential also indicates an optimum value of 41.3 mV for the NS/water of 1.08% which corresponds to the mix proportion of C-06. Both the compressive strength and zeta potential verify an optimum added amount of NS of 0.6%. Due to alkalinity of the cement hydration products of CSH and Ca(OH)2 , the relationship of zeta potentials and pH values from 7 to 12 investigated at 1.08% of NS/water ratio is shown in Fig. 3. The absolute values of zeta potential gradually increase with the increase of pH values. As a result, under alkali environment, the dispersion mechanism of nanosilica performs quite well.

Fig. 3. Zeta potential at various pH values.

Fig. 4. NMR curve of Portland cement.

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Fig. 5. NMR curves of hardened Portland cement composite: (a) without NS and (b) with NS.

tion was adopted. A general Lorentzian function y(x) can be expressed as Eq. (2) [16]: y(x) = y0 + W 2A 4(x xc )2 + W 2 (2)

where x is the chemical shift (ppm) in NMR, y(x) the intensity, y0 the datum of the peak, A the area covered by the curve, xc the location of peak and W is the full-width-at-half-maximum (FWHM). The values of these four parameters, y0 , A, xc and W, for three NMR curves in Figs. 4 and 5a and b, can be obtained through the least-square curve-tting technique, and listed in Table 4. The coefcients of determination of R2 for these three curves are 0.972, 0.989 and 0.992, respectively, indicating a relatively satisfactory strength of the linear association between independent variable x and dependent variable y. The locations of peak intensities, Q0 , Q1 and Q2 in Table 4 are close to those values of 70, 80 and 88 ppm. The tted curves of Lorentzian function are also drawn in Figs. 4 and 5a and b. The degree of hydration of cement-based composite, , can be estimated on the base of values of Q0 through the following equation [17]: (%) = 1 I(Q0 ) 100 I 0 (Q0 ) (3)

and 73.17%, respectively. Thus, at the age of 56 days, the degree of hydration of hardened cement composite with NS increases by about 2.8% by comparison with the pure hardened cement paste. Meanwhile, the ratio of A value of Q2 to that of Q1 can be served as an index to indicate the relative quality of Portland cement composite in which a higher value means better mechanical properties [18]. The ratio calculated from the values of A of Q2 and Q1 in Table 4 increases from 0.0806 to 0.2927. Thus, this result conrms a positive improvement on the compressive strengths of cement composite due to the addition of NS based on the experimental results as stated in the previous section. Furthermore, the variation of W (FWHM) values at Qn peaks can also be used to evaluate the amorphous character of microstructure of hardened cement paste [19]. After the addition of NS, the FWHM value of Q1 peak in cement composite reduces substantially by about 29.23%, indicating that the arrangement order of OSiO net seems to become regular with a pattern of sharing a common oxygen atom. Therefore, both the increases of and Q2 /Q1 and the decrease of FWHM indeed conrm the improvement of microstructures of hydrated cement composite as a result of the addition of NS. 3.3.2. BET examination The BrunauerEmmettTeller (BET) technique is primarily used to measure the surface area of a solid from the physical adsorption of a gas, such as nitrogen N2 , on the solid surface, particularly suitable for materials like hydrated Portland cement paste with apparent open porosity [20]. The BET equation that computes the number of adsorbed gas molecules from

where I(Q0 ) is the A value of Q0 for the hydrated cement-based composite and I0 (Q0 ) the A value of Q0 for the Portland cement powder. Substituting the A values of 57996.43, 52532.62 and 195769.26 in Table 4 into Eq. (3) gives the values of of 70.38%
Table 4 Values of four constants of Lorentzian functions for three NMR curves Portland cement powder Qn y0 xc A W R2 Q0 0 71.26 195769.3 5.15 0.972 Pure hardened Portland cement paste Q0 0 71.06 57996.4 1.65 0.989 Q1 79.48 175894.7 9.58 Q2 84.05 14170.4 3.12

Hardened Portland cement composite with NS Q0 0 70.39 52532.6 2.58 0.992 Q1 77.92 133362.9 6.78 Q2 82.70 39033.9 3.98

Note: R2 denotes the coefcient of determinant dened as the ratio of sum of squares due to regression to the total sum of squares.

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the adsorption isotherms of nitrogen N2 is given as follows [21]: P 1 C1 = + P W(P0 P) Wm C Wm CP0 (4)

where P0 is the saturation pressure of the adsorbate, P the equilibrium pressure of the adsorbate, W the weight of nitrogen adsorbed at a given P/P0 , Wm the weight of a monolayer of adsorbate, and C is the constant related to the heat of adsorption. A linear relationship between 1/W[(P0 /P) 1] and P/P0 is required to obtain the quantity of nitrogen adsorbed. The slope a and intercept b are used to determine the quantity of nitrogen adsorbed in the monolayer, Wm , by the following equation: Wm = 1 a+b (5)

where s is a material parameter. In order to conform to the physical meaning of a surface, the range of D should be between 2 (smooth surfaces) and 3 (all available porosities being occupied). In other words,1 < s <0 is essential for Eq. (7). The value of s can be estimated through the FrenkelHalseyHill equation shown as follows [25]: log P0 P = B Vs (8)

where P0 and P are the same as those in Eq. (4), V the amount of adsorption, and B is the another constant accounting for the interaction between the adsorbent and adsorbate. The value of s can be obtained as the slope of a linear equation in Eq. (9) transformed from Eq. (8): log log P0 P = log B s log V (9)

Then, the specic surface area of the sample, S, can be calculated as S= Wm NA Acs Mw (6)

where NA is Avogadros number (6.023 1023 molecules/mol), Acs the molecular cross-sectional area (77 K nitrogen N2 16.2 A2 ), M the molecular weight of adsorbate (nitrogen N2 28.0134 g/mol), and w is the sample weight. The intercept a and the slope b for the experimental BET data in this study were founded to be 1.517 and 147.98 for the hardened Portland cement paste, and 0.209 and 137.0 for the hardened cement composite with NS, respectively, as shown in Fig. 6a and b. From Eq. (6), the specic surface area increases from 23.30 m2 /g for the hardened Portland cement paste to 25.38 m2 /g for the hardened cement composite with NS by 8.95%. To estimate the surface characteristics of hardened Portland cement composite, an index often referred to as fractal dimension D determined from adsorption data was used in this study [2224]. One kind of the fractal dimension value D is dened as given in Eq. (7) [24]: D=3+s (7)

plots of log V verses log(log(P0 /P)) for the experimental BET curves are presented in Fig. 7a and b from which the values of s for the hardened Portland cement paste and cement composite with NS were found to be 0.4977 and 0.3805, respectively. From Eq. (7), the values of fractal dimension D become 2.502 and 2.620, respectively, indicating an improvement on the surface roughness. Therefore, both the surface area and fractal dimension conrm that the hardened Portland cement composite with NS has denser microstructures. 3.3.3. MIP examination Mercury intrusion porosimetry is based on the capillary law governing liquid penetration into minor pores. This law is expressed by the modied Washburn equation [26]: d= cos p (10)

where is the shape factor, d the narrow dimension of pore, the surface tension, the contact angle and p is the applied pressure. In respect to mercury liquid and oven-dried Portland cementbased materials, the values of surface tension and contact angle

Fig. 6. BET plots of hardened Portland cement composite: (a) without NS and (b) with NS.

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Fig. 7. FHH plots of hardened Portland cement composite: (a) without NS and (b) with NS.

were taken as 117 and 0.484 N/m, respectively [27,28]. Moreover, according to the observation of Maage [29] as well as the report of Cook and Hover [30], the value of shape factor is assumed to be 4 in terms of the circular cross section of cylindrical pore. Therefore, Eq. (10) can be rewritten as follows: d= 878.93 p (11)

shifts to ner pore sizes. Therefore, both the decrease of pore volume and smaller pore size distribution indicate that the hardened Portland cement composite with NS has a more consolidated microstructure. A fractal dimension D* based on the pore size distribution can be computed with the following Eqs. (12) and (13) deducted by Ji et al. [31]: log V = C + k log d D = 3 k (12) (13)

where d is the pore entry diameter in nm, p the applied pressure in MPa. Eq. (11) was used to convert a given applied pressure to a specic pore diameter for the experimental MIP data. Two types of experimental MIP plots can be obtained. One plot is the cumulative pore volume verses the pore diameter as shown in Fig. 8a and b, and the other is the distributive pore volume verses pore diameter as presented in Fig. 9a and b. Both Fig. 8a and b show that total pore volume decreases from 0.2435 ml/g for pure hardened cement paste to 0.2382 ml/g for hardened cement composite with NS by 2.18%. Also its curvatures of cumulative curve become slightly greater. By comparison with Fig. 9a, the pore size distribution shown in Fig. 9b

where V* is the cumulative pore volume in percentage, C and k are constants to be found, and d is the pore entry diameter in nm same as in Eq. (11). Using Eqs. (12) and (13), the experimental MIP data are plotted in Fig. 10a and b. Note that, since the cumulative pore volume ratio V* at the maximum log V* pore entry diameter is assumed to be 100, it is the corresponding value of becomes 2 as shown in these two gures. According to the locations at the changes of slope for the curves in Fig. 10a and b, the abscissa is roughly divided into three zones AC, where zone

Fig. 8. Accumulated MIP pore volume of hardened Portland cement composite: (a) without NS and (b) with NS.

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Fig. 9. MIP pore distribution of hardened Portland cement composite: (a) without NS and (b) with NS.

Fig. 10. Relationship between log V* and log d of Portland cement composite: (a) without NS and (b) with NS.

A denotes the pore size smaller than 10 nm, zone B the pore sizes between 10 and 100 nm and zone C the pore size larger than 100 nm. For each zone, an individual least-square linear model to t the test data was conducted to obtain the slope k in Eq. (12) and thus the value of D* in Eq. (13). These calculated values are presented in Table 5, where the percentages of partial volumes between bounds of each individual neighboring zone computed by the difference of V* are also illustrated. After adding NS into cement composite, the partial volume ratio Vp

at zone A increases by 1.22%, whereas decreases by 1.21% and 0.01% for zones B and C, respectively. On the contrary, the value of D* decreases from 1.567 to 1.517 for zone A, but increase from.2.261 to 2.305 for zone B and from 2.991 to 2.993 for zone C, respectively. These results indicate that the microstructure of hardened cement composite with NS becomes denser at the regions where the pore size is larger than 10 nm, but becomes looser at the regions where the pore size is smaller than 10 nm.

Table 5 Values of slope k, fractal dimension D* and volume ratio VP at three zones Pure hardened Portland cement paste Zone Range k D* Vp V* A B <10 nm 10100 nm 1.433 0.739 1.567 2.261 14.84% 79.31% V* (<10 nm): 14.84%; V* (<100 nm): 94.15% C >100 nm 0.009 2.991 5.85% Hardened Portland cement composite with NS A B <10 nm 10100 nm 1.483 0.695 1.517 2.305 16.06% 78.10% V* (<10 nm): 16.06%; V* (<100 nm): 94.16% C >100 nm 0.007 2.993 5.84%

Note: V* = accumulated volume ratios.

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4. Conclusions Based on the experimental results and microstructural analyses presented in this study, the following conclusions can be drawn: (1) Among four ages and ve sets of mix proportions, the optimal mix proportion is the set of cement:water:nanosilica = 1:0.55:0.006 which has the highest compressive strength of 65.62 MPa at age of 56 days. By comparison with the control set of cement paste without the addition of nanosilica, the ratio of maximum increase in compressive strength is about 60.6% at age of 14 days and reduces to 43.8% at age of 56 days. (2) Among four sets of mix proportions, the zeta potential for the optimum mix set of nanosilica/water of 1.08% by weight has a maximum absolute value of 41.3 mV. This optimal mixture set obtained by zeta potential test is corresponding to the mix proportion of cement composite in the compressive test. Thus, the test results of zeta potential suggest that this test method may be able to serve as a quick and easy preliminary technique to select quantitatively the optimal mix proportion of cement composite with addition of nanosilica simply by using the paste mixing the nanosilica with water. (3) The observation on the changes of test values for these indices of , Q2 /Q1 , and FWHM obtained from the NMR analyses, has shown that the microstructures of Portland cement composite added with nanosilica become more stable and stronger bonding. (4) Both the surface area and the fractal dimension deducted by BET experiment also conrm a denser microstructure for the hardened cement composite with the addition of nanosilica. (5) The Portland cement composite incorporating nanosilica measured by MIP technique reveals that the pore volume increases and the fractal dimension of microstructure decreases at regions where the pore size smaller than 10 nm, but the results are opposite for regions where the pore size larger than 10 nm. Acknowledgments The authors thank the National Science Council of Taiwan, Republic of China for nancial support of this work (Grant NSC-

92-2211-E-011-052). Courtesy of some experimental data from Mr. Kuo-Ming Yang is also appreciated. References
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