Construction and Building Materials 25 (2011) 608616

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Pore structure and chloride permeability of concrete containing nano-particles for pavement
Mao-hua Zhang a,b,, Hui Li b
a b

School of Civil Engineering, Northeast Forestry University, 150040 Harbin, China School of Civil Engineering, Harbin Institute of Technology, 150090 Harbin, China

a r t i c l e

i n f o

a b s t r a c t
Pore structure and chloride permeability of concrete containing nano-particles (TiO2 and SiO2) for pavement are experimentally studied and compared with that of plain concrete, concrete containing polypropylene (PP) bers and concrete containing both nano-TiO2 and PP bers. The test results indicate that the addition of nano-particles renes the pore structure of concrete and enhances the resistance to chloride penetration of concrete. The rened extent of pore structure and the enhanced extent of the resistance to chloride penetration of concrete are increased with the decreasing content of nano-particles. The pore structure and the resistance to chloride penetration of concrete containing nano-TiO2 are superior to that of concrete containing the same amount of nano-SiO2. However, for the concrete containing PP bers, the pore structure is coarsened and the resistance to chloride penetration is reduced. The larger the content of PP bers, the coarser the pore structure of concrete, and the lower the resistance to chloride penetration. For the concrete containing both nano-TiO2 and PP bers, the pore structure is coarser and the resistance to chloride penetration is lower than that of concrete containing the same amount of PP bers only. A hyperbolic relationship between chloride permeability and compressive strength of concrete is exhibited. There is an obvious linear relationship between chloride permeability and pore structure of concrete. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 21 March 2010 Received in revised form 26 July 2010 Accepted 28 July 2010

Keywords: Nano-particles Pore structure Chloride permeability Polypropylene (PP) bers Pavement concrete

1. Introduction Concrete durability has attracted a lot of attention from many researchers, because it has critical inuence on the service life of concrete structure. Pavement is subjected to a harsh environment because of exposure in air and endures dynamic fatigue loads due to passing vehicles, and thus the durability of pavement concrete has received more attention. The durability properties of pavement concrete include many aspects such as permeability, impact resistance, abrasion resistance and frost resistance. In this study, the durability of pavement concrete is measured through permeability. Permeability, which can be dened as the ease with which external media such as liquids, gases, various aggressive ions and other pollutants penetrate concrete [1,2], is considered to be one of the most important properties affecting concrete durability [3]. A lower permeability reduces the ingress and movement of uid media in concrete and is therefore benecial. Concrete with higher permeability allows faster penetration of uid media, resulting in rapid deterioration of concrete.

Corresponding author at: School of Civil Engineering, Northeast Forestry University, 150040 Harbin, China. Tel./fax: +86 451 86282027. E-mail address: zmh7716@163.com (M.-h. Zhang).
0950-0618/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2010.07.032

Concrete is a heterogeneous and porous material, in which there are many pores with different sizes and shapes. It is well known that the pore structure of concrete strongly inuences its physical properties. Many important properties, such as strength and permeability, are directly or indirectly related to the pore structure of concrete [4,5]. It is generally agreed that the pore structure of concrete is one of its most important characteristics and strongly affects both its durability and mechanical properties [6]. Therefore, study of the pore structure of concrete is essential to understand the nature of this complex material. The permeability of concrete, which is strongly affected by the pore structure of concrete, is now accepted mainly to be a function of pore size distribution [4]. The permeability of concrete is intimately related to the pore connectivity, but the compressive strength of concrete is governed by the total porosity [5,7]. The permeability of concrete mostly lies on the pore structure and its development and change. There are three types of factors affecting the permeability of concrete [8]. The rst one is the factors that inuence the original pore structure of concrete such as water-to-binder ratio, mineral admixtures (such as silica fume, y ash and blast furnace slag) and additive agents (such as water-reducing agent, air-entraining agent and expansive agent). The second one is the factors that affect the development of pore structure of concrete including the curing condition, age and the

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

609

activity of binder. The third one is the penetration condition such as hydraulic gradient, penetration time and chemistry component of penetration media. There are two types of arguments regarding the relationship between compressive strength and permeability of concrete. Some researchers consider that compressive strength is a crucial factor affecting the permeability of concrete, and the permeability of concrete decreases with increasing compressive strength. For instance, Mohr et al. [1] described the relationship between compressive strength and permeability of concrete by a power function, and a similar trend was found by Armaghani et al. [9]. While other researchers consider that there is no signicant relationship between compressive strength and permeability of concrete, and the compressive strength of concrete cannot reect its permeability, especially for high-performance concrete [7]. Many studies have shown that the addition of PP bers is harmful to the impermeability of concrete. Toutanji et al. [10,11] found that the permeability of concrete containing PP bers is enhanced, and this was attributed to that PP bers increased the void content in concrete due to the lack of cohesiveness of cement matrix and poor dispersion of PP bers. However, there are also many researchers who argued that the impermeability of concrete was signicantly improved by the addition of PP bers [12,13]. By the addition of mineral admixtures such as silica fume, the impermeability of concrete is increased to some extent. Toutanji [11] and Oh et al. [14] reported that the permeability of concrete containing silica fume was remarkably reduced because of the denser pore structure. Toutanji et al. [10] also indicated the addition of silica fume improved the dispersion of PP bers in cement matrix, causing a marked reduction in the permeability of PP ber-reinforced concrete. Nano-materials have been considered as the most promising materials in 21 century by scientists. In recent years, much attention has been paid to the applications of nano-materials in civil engineering, because nano-particles possess many special properties such as huge specic surface area and high activity due to their small size. Li et al. [15,16] investigated the improvement in compressive and exural strengths, abrasion resistance, and exural fatigue performance of concrete containing nano-particles. Li et al. [17,18] also studied the microstructure and self-sensing properties of mortar containing nano-particles. The results show good prospects of concrete (or mortar) containing nano-particles. In cold area, deicing salt is often used to sprinkle on pavement after snowing and icing. Pavement concrete may fail due to the penetration of chloride, so the permeability measured by chloride ion is more consistent with the practical condition of pavement concrete. In this work, the pore structure and chloride permeability of concrete containing nano-particles (TiO2 and SiO2) for pavement is experimentally studied and compared with that of plain concrete, concrete containing PP bers and concrete containing both nano-TiO2 and PP bers.
2. Experimental program 2.1. Materials and mixture proportions The cement used is Portland cement (P.O42.5). The ne aggregate is natural river sand with a neness modulus of 2.4. The coarse aggregate used is crushed diabase with a diameter of 530 mm. The properties of nano-particles (TiO2 and Table 1 Properties of nano-particles. Item SiO2 TiO2 Diameter (nm) 10 5 15 Specic surface area (m2/g) 640 50 240 50

Table 2 Properties of modied PP bers. Elongation (%) 40 3 Titer (D) 11 0.5 Diameter (lm) 8492 Length (mm) 15 1

SiO2) are given in Table 1. The properties of modied PP bers used are shown in Table 2. The water-reducing agent (UNF-5, one kind of b-naphthalene sulfonic acid and formaldehyde condensates) is employed to aid the dispersion of nano-particles in cement paste and achieve good workability of concrete. The defoamer (tributyl phosphate) is used to decrease the amount of air bubbles. The water-to-binder (the sum of cement and nano-particles) ratio used for all mixtures is 0.42, and the sand ratio is 34%. The mixture proportions of concretes per cubic meter are given in Table 3. Here, PC denotes plain concrete. PPC6 and PPC9 denote the concrete containing PP bers in the content of 0.6 and 0.9 kg/ m3, respectively. NSC1 and NSC3 denote the concrete containing nano-SiO2 in the amount of 1% and 3% by weight of binder, respectively. NTC1, NTC3 and NTC5 denote the concrete containing nano-TiO2 in the amount of 1%, 3% and 5% by weight of binder, respectively. NTPC denotes the concrete containing both nano-TiO2 in the amount of 1% by weight of binder and PP bers in the content of 0.9 kg/m3. 2.2. Specimen preparation To prepare the concrete containing nano-particles, water-reducing agent is rstly mixed into water in a mortar mixer, and then nano-particles are added and stirred at a high speed for 5 min. Defoamer is added as stirring. Cement, sand and coarse aggregate are mixed at a low speed for 2 min in a concrete centrifugal blender, and then the mixture of water, water-reducing agent, nano-particles and defoamer is slowly poured in and stirred at a low speed for another 2 min to achieve good workability. To prepare plain concrete and the concrete containing PP bers, waterreducing agent is rstly dissolved in water. After cement, sand, coarse aggregate and PP bers (if used) are mixed uniformly in a concrete centrifugal blender, the mixture of water and water-reducing agent is poured in and stirred for several minutes. Finally, the fresh concrete is poured into oiled molds to form cubes of size 100 100 100 mm to be used for compressive strength and permeability testing, prisms of size 100 100 400 mm for exural strength and pore structure testing. After pouring, an external vibrator is used to facilitate compaction and reduce the amount of air bubbles. The specimens are de-molded at 24 h and then cured in a room at a temperature of 20 3 C and a relative humidity of 95% until the prescribed period. 2.3. Test methods Both compressive and exural tests are performed according to JTG E30-2005 (Test Methods of Cement and Concrete for Highway Engineering, China). 2.3.1. Pore structure measurement There are many methods usually used to measure the pore structure, such as optics method, mercury intrusion porosimetry (MIP), helium ow and gas adsorption [19]. MIP technique is extensively used to characterize the pore structure in porous material due to its simplicity, quickness and wide measuring range of pore diameter [5,19]. MIP also provides the information about pore connectivity [19]. In this study, the pore structure of concrete is determined by using MIP. To prepare the samples for MIP measurement, the concrete specimens after the specied curing ages are rst broken into smaller pieces, and then the cement paste fragments selected from the center of prisms are used to measure pore structure. The samples are immersed in acetone to stop hydration as fast as possible. Before mercury intrusion test, the samples are dried in an oven at about 105 C to remove moisture in the pores until a constant weight is achieved. MIP is based on the assumption that the nonwetting liquid mercury (the contact angle between mercury and solid is greater than 90) will only intrude in the pores of porous material under pressure [5,19]. Each pore size is quantitatively determined from the relationship between volume of intruded mercury and applied pressure [5]. The relationship between pore diameter and applied pressure is generally described by Washburn equation as follows [5,19].

D 4c cos h=P

Density (kg/m3) <120 4060

Purity (%) 99.9 99.7

Phase Anatase

610 Table 3 Mix proportions of concretes (unit: kg/m3). Mixture type PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC Water 151 151 151 151 151 151 151 151 151 Cement 360 360 360 356.4 349.2 356.4 349.2 342 356.4

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

Sand 650 650 650 650 650 650 650 650 650

Coarse aggregate 1260 1260 1260 1260 1260 1260 1260 1260 1260

PP ber 0.6 0.9 0.9

Nano-SiO2 3.6 10.8

Nano-TiO2 3.6 10.8 18 3.6

UNF-5 5.4 5.4 5.4 5.4 7.2 5.4 7.2 7.2 7.2

Defoamer 0.216 0.288 0.216 0.288 0.288 0.288

Slump (mm) 5060 3040 2030 2030 1020 2030 2030 1020

where D is the pore diameter (nm), c is the surface tension of mercury (dyne/cm), h is the contact angle between mercury and solid (), and P is the applied pressure (MPa). The test apparatus used for pore structure measurement is AutoPore IV 9500 type. The density of mercury is 13.5335 g/mL. The surface tension of mercury is taken as 485 dynes/cm, and the contact angle selected is 130. The maximum measuring pressure applied is 220 MPa (33000 psia), which means that the smallest pore diameter that can be measured reaches about 5 nm (on the assumption that all pores have cylindrical shape).

Di

RT ri Z2 F 2 Ci i

where Di is the diffusivity of particle i (cm2/s); R is the gas constant (8.314 J/(mol K)); T is the absolute temperature (K); ri is the partial conductivity of particle i (S/cm); Zi is the charge of particle i; F is the Faradays constant (96,500 Coul/mol); Ci is the concentration of particle i (mol/cm3). If the partial conductivity ri and the concentration Ci have been determined, the diffusivity of particle i, Di can be calculated from Eq. (2). The partial conductivity ri is

2.3.2. Permeability measurement For permeability testing, conventional permeability test methods (e.g. water permeability test or gas permeability test) cannot be applied to high-strength and high-performance concrete because they are so dense and impermeable [14]. Permeability is one of the intrinsic properties of concrete and is only associated with the structural and chemical properties of concrete, not the media studied [20]. Therefore, taking into account the inuence of deicing salt on pavement concrete, the rapid chloride permeability test methodNEL method [20] is adopted in this study, because the resistance to chloride penetration is one of the simplest measures to determine the durability of concrete [14]. The specimens for chloride permeability testing are obtained by sawing the cubic specimens of size 100 100 100 mm into two slices of about 50 mm thickness. The slices are washed thoroughly and then put in a vacuum box shown in Fig. 1a to expel all air from the internal voids. After the vacuum suction is maintained for 6 h at the vacuum level of 0.06 to 0.09 atm, saturated NaCl solution with a concentration of 4 mol/L is injected into the vacuum box and the slices are submerged in brine for 18 h so that all the voids are lled with brine. Finally, the slices are taken out and sandwiched between two copper electrodes shown in Fig. 1b under an 8 V low voltage. Partial conductivity of concrete is measured and the NernstEinstein equation is used to calculate the chloride diffusion coefcient [20].

ri ti r

where r is the conductivity of concrete; ti is the transference number of particle i, which is dened as

ti

Q i Ii Q I

where Qi and Ii is the electric quantity and current contribution of particle i to the total electric quantity Q and current I, respectively.

3. Test results and discussion 3.1. Compressive and exural strengths Table 4 shows the compressive and exural strengths of concretes at 28 days. It can be seen that both the compressive and exural strengths of concretes can be increased when nano-particles in a small amount are added; however, when nano-particles in a large

(a) Vacuum box, control device and vacuum pump

(b) Specimen clamp

Fig. 1. Instrument used in the chloride permeability test.

Table 4 Compressive and exural strengths of concretes. Mixture type Flexural strength Value (MPa) PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC 5.46 5.99 6.60 5.69 5.36 6.02 5.62 5.28 4.85 Variation coefcient (%) 6.29 3.77 5.51 3.97 6.78 4.20 4.28 6.00 7.79 Enhanced extent (%) 0 9.81 20.87 4.21 1.87 10.28 3.04 3.27 11.21 Compressive strength Value (MPa) 59.08 61.02 63.29 66.36 61.16 69.73 66.62 60.00 55.84 Variation coefcient (%) 3.16 6.71 3.44 4.15 5.96 5.47 6.12 4.93 7.38 Enhanced extent (%) 0 3.28 7.12 12.31 3.51 18.03 12.76 1.55 5.48

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

611

Log differential volume dV/dlogD (mL/g)

amount are added, e.g. NSC3 and NTC5, the exural strengths of concretes are lower than that of plain concrete although the compressive strengths are slightly increased. The effectiveness of nano-TiO2 in enhancing compressive and exural strengths of concretes increases in the order: NTC5 < NTC3 < NTC1 (with the decrease on nano-TiO2 content), and the similar results can be found for the concretes containing nano-SiO2. That is to say, the enhanced extent of concrete strengths reduces with the increasing content of nano-particles. Furthermore, the compressive and exural strengths of concretes containing nano-SiO2 are smaller than that of concretes containing the same amount of nano-TiO2. The larger the content of PP bers, the higher compressive and exural strengths of concrete. When the content of PP bers increases from 0.6 to 0.9 kg/m3, the compressive strength of concrete containing PP bers enhances slightly, but the exural strength improves signicantly. If concrete is homogeneous and has no aws, its compressive and exural strengths should be increased synchronously. But in practice, the enhanced extent of compressive strength of concrete is greatly larger than that of exural strength. This can be attributed to the presence of microcracks with different scales in concrete, and the effect of microcracks on exural strength of concrete is greater than on compressive strength [21]. When the content of nano-particles is larger, e.g. NSC3 and NTC5, the slump of concrete becomes lower as shown in Table 3, and the number of microcracks in concrete increases, which results in the decrease of exural strength of concrete. In addition, because the uniform dispersion of nano-particles in cement paste is difcult when the content of nano-particles is large, the weak zone (the conglomeration of nano-particles) in concrete increases [17], which also leads to the decrease of exural strength of concrete. With the addition of PP bers, the propagation of microcracks is inhibited and the scale of microcracks is reduced due to the crack-arresting effect, crackthinning effect and crack-bridging effect of PP bers [21,22], so the enhanced extent of exural strength of concrete containing PP bers is higher than that of compressive strength. The larger the content of PP bers (when the content of PP bers increases from 0.6 to 0.9 kg/m3), the stronger these effects (crack-arresting effect, crack-thinning effect and crack-bridging effect). The compressive and exural strengths of concretes containing nano-SiO2 are lower than that of concretes containing the same amount of nano-TiO2, which is primarily attributed to the fact that the particle diameter (shown in Table 1) of nano-SiO2 is smaller than that of nano-TiO2, and the specic surface area (shown in Table 1) of nano-SiO2 is much larger than that of nano-TiO2, so that it is more difcult to uniformly disperse than nano-TiO2 in cement matrix. For the concrete containing both nano-TiO2 (1%) and PP bers (0.9 kg/m3), its compressive and exural strengths are both decreased, which indicates that the hybrid addition of nano-TiO2 and PP bers has a negative effect on the compressive and exural strength of concrete. When nano-TiO2 (1%) and PP bers (0.9 kg/ m3) are respectively added into concrete, the slump of fresh concretes is lower than that of plain concrete; when the concrete contains both nano-TiO2 and PP bers, its slump becomes more lower, which makes the density of hardened concrete decreased and the void content in concrete increases, so the compressive and exural strengths are reduced. 3.2. Pore structure The test results of MIP in this study include the pore structure parameters such as total specic pore volume, most probable pore diameter, pore size distribution, porosity, average diameter, and median diameter (volume).

In terms of the different effect of pore size on concrete performance, the pore in concrete is classied as harmless pore (<20 nm), less-harmful pore (2050 nm), harmful pore (50 200 nm) and more-harmful pore (>200 nm) [8]. In order to analyze and compare conveniently, the pore system of concrete is divided into four ranges according to this sort method in this study. 3.2.1. Total specic pore volume and most probable pore diameter of concrete The integral and differential curves of pore size distribution of concrete can be drawn from the data of MIP, and the two curves can show the pore network of concrete. Fig. 2 shows the integral curves of pore size distribution of concretes. The peak value of integral curve denotes the total specic pore volume of concrete, which is the total volume of mercury intruded into the sample with a mass of 1 g. The larger the total specic pore volume, the coarser the pore structure. Fig. 3 presents the differential curves of pore size distribution of concretes. The diameter corresponding to the peak value of differential curve is regarded as the most probable pore diameter, which is the diameter whose size occupies the largest proportion of pores compared with other pore diameters. The smaller the most probable pore diameter, the ner the pore structure. The total specic pore volumes and most probable pore diameters of various concretes are analyzed and compared, and the results are given in Table 5. It can be seen from Figs. 2 and 3, and Table 5 that with the addition of nano-particles, the total specic pore volumes of concretes decrease, and the most probable pore diameters of concretes shift to smaller pores and fall in the range of less-harmful pore, which indicates that the addition of nano-particles renes the pore structure of concretes. The effectiveness of nano-TiO2 in reducing the total specic pore volumes and most probable pore diameters of concretes

Cumulative volume V (mL/g)

0.06 0.05 0.04 0.03 0.02 0.01 0.00 7000

PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC

1000 100 Pore diameter D (nm)

10

Fig. 2. Integral curves of pore size distribution of concretes.

0.06 0.05 0.04 0.03 0.02 0.01 0.00 7000

PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC

1000

100

10

Pore diameter D (nm)

Fig. 3. Differential curves of pore size distribution of concretes.

612

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

Table 5 Total specic pore volumes and most probable pore diameters of concretes. Mixture type Total specic pore volume Value (mL/g) PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC 0.0534 0.0557 0.0578 0.0501 0.0515 0.0470 0.0496 0.0510 0.0592 Reduced extent (%) 0 4.31 8.24 6.18 3.56 11.99 7.12 4.49 10.86 Most probable pore diameter Value (nm) 47 51 54 40 44 32 39 43 57 Reduced extent (%) 0 8.51 14.89 14.89 6.38 31.91 17.02 8.51 21.28

increases in the order: NTC5 < NTC3 < NTC1, and the similar results can be observed for the concretes containing nano-SiO2. The pore structure of NTC1 is rened most signicantly, and the total specic pore volume and most probable pore diameter decrease by 12% and 31.91%, respectively. With the increasing content of nano-particles, the reduced extent of total specic pore volume and most probable pore diameter decreases, and the renement on pore structure of concretes is weakening. The pore structure of concretes containing nano-TiO2 is ner than that of concretes containing the same amount of nano-SiO2. The total specic pore volume and most probable pore diameter of NSC1 are close to those of NTC3, and the total specic pore volume and most probable pore diameter of NSC3 are close to those of NTC5. By the addition of PP bers, the total specic pore volumes of concretes increase, and the most probable pore diameters of concretes shift to larger pores and fall in the range of harmful pore, which shows that the addition of PP bers coarsens the pore structure of concretes. Moreover, with the increasing content of PP bers, the total specic pore volume and most probable pore diameter of concrete increase and the pore structure of concrete becomes coarser.

For the concrete containing both nano-TiO2 and PP bers, the total specic pore volume also increases, and the most probable pore diameter also shifts to larger pore and falls in the range of harmful pore. The enhanced extent of total specic pore volume and most probable pore diameter of NTPC is obviously larger than that of concrete containing the same amount of PP bers only, which indicates that the hybrid addition of nano-TiO2 and PP bers makes the pore structure of concrete coarser. Table 6 gives the porosities, average diameters and median diameters (volume) of various concretes. The regularity of porosity is similar to that of total specic pore volume. The regularity of average diameter and median diameter (volume) is similar to that of most probable pore diameter. Therefore, the details are not given herein.

3.2.2. Pore size distribution of concrete The pore size distribution of concretes is shown in Table 7. Fig. 4 shows the percent of specic pore volume of various grade pore size accounting for total specic pore volume. It can be seen that by the addition of nano-particles, the amounts of harmless and less-harmful pores in concretes increase, and the amounts of

Table 6 Porosities, average diameters and median diameters (volume) of concretes. Mixture type Porosity Value (%) PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC 11.10 11.49 11.90 10.33 10.80 9.22 10.23 10.71 12.52 Reduced extent (%) 0 3.55 7.24 6.93 2.66 16.89 7.85 3.53 12.82 Average diameter Value (nm) 41.7 43.1 44.3 37.8 40.1 35.6 37.4 39.9 51.2 Reduced extent (%) 0 3.36 6.24 9.35 3.84 14.63 10.31 4.32 22.78 Median diameter (volume) Value (nm) 57.1 59.4 62.8 49.8 54.6 45.8 49.4 54.2 66.3 Reduced extent (%) 0 4.03 9.98 12.78 4.38 19.79 13.49 5.08 16.11

Table 7 Pore size distribution of concretes. Mixture type Pore size distribution (mL/g) Harmless pores (<20 nm) PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC 0.0072 0.0071 0.0070 0.0075 0.0075 0.0073 0.0075 0.0074 0.0071 Less-harmful pores (2050 nm) 0.0163 0.0162 0.0160 0.0179 0.0166 0.0183 0.0178 0.0168 0.0155 Harmful pores (50200 nm) 0.0188 0.0200 0.0211 0.0157 0.0171 0.0136 0.0156 0.0168 0.0220 More-harmful pores (>200 nm) 0.0111 0.0124 0.0137 0.0092 0.0104 0.0079 0.0089 0.0100 0.0147 Total specic pore volume (mL/g)

0.0534 0.0557 0.0578 0.0503 0.0516 0.0471 0.0498 0.0510 0.0593

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

613

40 35 30 25 20 15 10 5 0 <20nm 20~50nm 50~200nm >200nm Pore size distribution

PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC

Fig. 4. Percent of specic pore volume of various grade pore size accounting for total specic pore volume.

harmful and more-harmful pores decrease, which shows that the density of concretes is increased and the pore structure is rened. The effectiveness of nano-TiO2 in rening the pore structure of concretes increases in the order: NTC5 < NTC3 < NTC1, and the similar results can be found for the concretes containing nanoSiO2. The harmless and less-harmful pores in NTC1 increase by the largest extent, while its harmful and more-harmful pores decrease by the largest extent, which indicates that the pore structure of NTC1 is most signicantly rened. With the increasing content of nano-particles, the enhanced extent of harmless and less-harmful pores and the reduced extent of harmful and moreharmful pores in concretes are both decreased, and the renement on pore structure of concretes is weakening. The pore size distribution of NSC1 and NTC3 is close to each other. The harmless and less-harmful pores in NTC3 are both more than that in NSC1; though the harmful pores in NTC3 are slightly more than that in NSC1, its more-harmful pores are less than that in NSC1. Therefore, the pore structure of NTC3 is slightly ner than that of NSC1. The pore size distribution of NSC3 and NTC5 is also close to each other. Although the harmless pores in NTC5 are less than that in NSC3, its less-harmful pores are more than that in NSC3, and the harmful and more-harmful pores in NTC5 are both less than that in NSC3. Therefore, the pore structure of NTC5 is slightly ner than that of NSC3. With the addition of PP bers, the amounts of harmless and less-harmful pores in concretes decrease, and the amounts of harmful and more-harmful pores increase, which shows that the density of concretes is reduced and the pore structure is coarsened. With the increasing content of PP bers, the reduced extent of harmless and less-harmful pores and the enhanced extent of harmful and more-harmful pores in concretes are both increased, and the pore structure of concrete becomes coarser and coarser. For the concrete containing both nano-TiO2 and PP bers, the harmless and less-harmful pores decrease by the largest extent, while its harmful and more-harmful pores increase by the largest extent. The pore structure of NTPC is obviously coarser than that of concrete containing the same amount of PP bers only, which indicates that the hybrid addition of nano-TiO2 and PP bers makes the pore structure of concrete further coarser.

cles and the distance between them are appropriate, the crystallization will be controlled in a suitable state through restricting the growth of Ca(OH)2 crystal by nano-particles. Moreover, nano-particles located in cement paste as kernel can further promote cement hydration due to their high activity. This makes the cement matrix more homogeneous and compact. Consequently, the pore structure of concrete is rened evidently such as the concrete containing nano-TiO2 in the amount of 1% by weight of binder. With the increasing content of nano-particles, the renement on pore structure of concrete is weakening. This can be attributed to that the distance between nano-particles decreases with the increasing content of nano-particles, and Ca(OH)2 crystal cannot grow up enough due to limited space and the crystal quantity is decreased, which causes the ratio of crystal to CSH gel to become small and the shrinkage and creep of cement matrix to increase [23], thus the pore structure of cement matrix is coarser relatively. The pore structure of concretes containing nano-SiO2 is coarser than that of concretes containing the same amount of nano-TiO2, which is mostly attributed to the fact that the particle diameter of nano-SiO2 is smaller than that of nano-TiO2, and the specic surface area of nano-SiO2 is much larger than that of nano-TiO2, so that the water demand of concrete containing nano-SiO2 is more than that of concrete containing the same amount of nano-TiO2. Consequently, when the mixture proportion of concrete is the same, nano-SiO2 is more difcult to uniformly disperse than nano-TiO2 in cement matrix, and is unable to exert its advantages. The pore structure of concrete containing PP bers is coarser than that of plain concrete, which can be attributed to the fact that the addition of PP bers increases the interface in concrete and results in the increase of void content (pore volume) in concrete [10]. The pore structure of concrete containing both nano-TiO2 and PP bers is the coarsest. When nano-TiO2 and PP bers are respectively added into concrete, the slump of fresh concrete is lower than that of plain concrete; when nano-TiO2 and PP bers are both added into concrete, the slump of fresh concrete further becomes lower. Because both nano-TiO2 and PP bers need water to envelop, and there is insufcient water used for the hydration of cement, therefore the pore structure of hardened concrete is coarse. To sum up, the addition of nano-particles renes the pore structure of concrete. On the one hand, nano-particles can act as a ller to enhance the density of concrete, which causes the porosity of concrete to reduce signicantly. On the other hand, nano-particles can not only act as an activator to accelerate cement hydration due to their high activity, but also act as a kernel in cement paste which makes the size of Ca(OH)2 crystal smaller and the tropism of Ca(OH)2 crystal more stochastic.

Ratio of specific pore volume of various grade pore size to total specific pore volume (%)

3.3. Chloride permeability 3.3.1. Test results of chloride permeability The test results for rapid chloride permeability of concretes at 28 days are presented in Table 8. It can be seen that the addition of nano-particles enhances the resistance to chloride penetration of concretes. The resistance to chloride penetration of concretes containing nano-TiO2 is higher than that of concretes containing the same amount of nano-SiO2. The effectiveness of nano-TiO2 in enhancing the resistance to chloride penetration of concretes increases in the order: NTC5 < NTC3 < NTC1. The resistance to chloride penetration of NTC1 increases by 31%. Even for NTC5, the resistance to chloride penetration also increases by 11.74%. The similar results can be observed for the concretes containing nano-SiO2, which indicates that the enhanced extent of the resistance to chloride penetration of concretes reduces with the increasing content of nano-particles.

3.2.3. Discussion The mechanism that nano-particles rene the pore structure of concrete can be interpreted as follows. Supposed that nano-particles are uniformly dispersed in concrete and each particle is contained in a cube pattern, the distance between nano-particles can be determined. After hydration begins, hydrate products diffuse and envelop nano-particles as kernel. If the content of nano-parti-

614 Table 8 Test results for chloride permeability of concretes. Mixture type PC PPC6 PPC9 NSC1 NSC3 NTC1 NTC3 NTC5 NTPC Chloride diffusion coefcient (1013 m2/s) 1.9356 2.1477 2.3198 1.5864 1.7326 1.3355 1.5554 1.7083 2.4393

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

Chloride diffusion coefficient (10-13m2/s)

2.4 2.2 2.0 1.8 1.6 1.4 1.2

Variation coefcient (%) 5.82 7.45 7.78 4.90 2.11 1.26 2.21 2.07 6.48

Reduced extent (%) 0 10.96 19.85 18.04 10.49 31.00 19.64 11.74 26.02

PC NSC1 NSC3 NTC1 NTC3 NTC5 NTPC

54

56

58

60

62

64

66

68

70

Compressive strength (MPa)

However, the resistance to chloride penetration of concretes containing PP bers decreases. The larger the content of PP bers, the lower the resistance to chloride penetration of concrete. The similar conclusion can be found in the literatures [10,11]. For the concrete containing both nano-TiO2 and PP bers, the resistance to chloride penetration is reduced signicantly, and even lower than that of concrete containing the same amount of PP bers only.
Fig. 5. Relationship between chloride diffusion coefcients and compressive strengths of concretes.

Table 9 Regression coefcients in Eq. (5). h1 2.0031 h2 88.1728 Correlation coefcient r 0.9624

Chloride diffusion coefficient (10-13m2/s)

2.6

2.6

Chloride diffusion coefficient (10-13m2/s)

0.048 0.051 0.054 0.057 0.060

2.4 2.2 2.0 1.8 1.6 1.4 1.2 0.045

2.4 2.2 2.0 1.8 1.6 1.4 1.2 30 35 40 45 50 55 60

Total specific pore volume (mL/g)

2.6
2.8

Most probable pore diameter (nm)

Chloride diffusion coefficient (10-13m2/s)

2.4 2.2 2.0 1.8 1.6 1.4 1.2 9 10 11 12 13

Chloride diffusion coefficient (10-13m2/s)

2.6 2.4 2.2 2.0 1.8 1.6 1.4 33 36 39 42 45 48 51 54

Porosity (%)
2.6

Average diameter (nm)

Chloride diffusion coefficient (10-13m2/s)

2.4 2.2 2.0 1.8 1.6 1.4 1.2 45 50 55 60 65 70

Median diameter (volume) (nm)

Fig. 6. Relationship between chloride diffusion coefcients and pore structure parameters of concretes.

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616

615

The enhancement or reduction of the resistance to chloride penetration is essentially due to the improvement or degeneration of pore structure of concretes. By the addition of nano-particles, the pore structure of concretes is rened, so the resistance to chloride penetration is enhanced. With different content of nano-particles, the change trend of the resistance to chloride penetration of concrete is entirely consistent with that of its pore structure. The pore structure of concretes containing nano-TiO2 is ner than that of concretes containing the same amount of nano-SiO2, so the resistance to chloride penetration of concretes containing nano-TiO2 is higher than that of concretes containing the same amount of nano-SiO2. The pore structure of concretes containing PP bers is coarsened, so the resistance to chloride penetration is reduced. With the increasing content of PP bers, the pore structure of concrete is coarser and coarser, so the resistance to chloride penetration becomes lower and lower. For the concrete containing both nano-TiO2 and PP bers, the pore structure is further coarser, so the resistance to chloride penetration decreases signicantly. 3.3.2. Relationship between chloride permeability and compressive strength of concrete At present, there is no agreement about the effect of compressive strength on the permeability of concrete as mentioned in Section 1. By nonlinear curve tting on the data of compressive strengths and chloride permeability of concretes, the relationship between chloride diffusion coefcients and compressive strengths of concretes, except the concretes containing PP bers only, is shown in Fig. 5. As mentioned in Section 1, the permeability of concrete is intimately related to the pore connectivity, but the compressive strength of concrete is governed by the total porosity [5,7]. Because PP bers do not participate in hydration and the addition of PP bers increases the interface in concrete, the resistance to chloride penetration of concretes containing PP bers is reduced, but the compressive strengths are slightly enhanced due to the crackarresting effect, crack-thinning effect and crack-bridging effect of PP bers [21,22]. There is no signicant relationship between chloride permeability and compressive strength of concretes containing PP bers. Fig. 5 indicates that the chloride diffusion coefcient of concrete decreases with increasing compressive strength. It can be observed that the curve approaches hyperbola basically, which conrms that the compressive strength is an important factor affecting the resistance to chloride penetration of concrete. The relationship between chloride diffusion coefcients and compressive strengths can be expressed by

Table 10 Regression coefcients in Eq. (6). Parameter of pore structure Total specic pore volume Most probable pore diameter Porosity Average diameter Median diameter (volume)

a
92.3371 0.0469 0.3746 0.0758 0.0556

b 3.0141 0.2567 2.2293 1.2624 1.2216

Correlation coefcient r 0.9991 0.9907 0.9803 0.9449 0.9892

It is observed from Fig. 6 that there is reasonably close correlation between chloride diffusion coefcients and pore structure parameters of concretes. The result of regression analysis can be written as follows

C dc a Pps b

where Cdc is the chloride diffusion coefcient (1013 cm2/s); Pps is the pore structure parameter; a and b are constants and presented in Table 10. It can be seen from Table 10 that there is signicant linear relationship between chloride diffusion coefcients and all pore structure parameters of concretes, and the correlation coefcients are basically larger than 0.95, which indicates that the resistance to chloride penetration of concretes is strongly inuenced by the pore structure. The ner the pore structure of concrete, the higher the resistance to chloride penetration of concrete. The total specic pore volume seems to be the parameter with the closest relation to chloride permeability.

4. Conclusions The following conclusions are drawn from this study: (1) The pore structure of concretes containing nano-particles is rened, and the rened extent is enhanced with the decreasing content of nano-particles. The pore structure of concretes containing nano-TiO2 is ner than that of concretes containing the same amount of nano-SiO2. The pore structure of concretes containing PP bers is coarsened, and becomes coarser and coarser with the increasing amount of PP bers. For the concrete containing both nano-TiO2 and PP bers, the pore structure is also coarsened and further becomes coarser than that of concrete containing the same amount of PP bers only. (2) The addition of nano-particles enhances the resistance to chloride penetration of concretes, and the enhanced extent is increased with the decreasing content of nano-particles. The resistance to chloride penetration of concretes containing nano-TiO2 is higher than that of concretes containing the same amount of nano-SiO2. The addition of PP bers reduces the resistance to chloride penetration of concretes. The larger the content of PP bers, the lower the resistance to chloride penetration of concrete. For the concrete containing both nano-TiO2 and PP bers, the resistance to chloride penetration is also decreased and even lower than that of concrete containing the same amount of PP bers only. (3) Except the concretes containing PP bers only, the relationship between chloride diffusion coefcients and compressive strengths of concretes approaches hyperbola basically, which indicates that the resistance to chloride penetration of concrete increases with increasing compressive strength. There is a signicant linear relationship between chloride permeability and pore structure of concretes. The ner the pore structure of concrete, the higher the resistance to chloride penetration of concrete.

C dc

fcu h1 fcu h2

where Cdc is the chloride diffusion coefcient of concrete (1013 cm2/s); fcu is the compressive strength (MPa); h1 and h2 are constants that can be obtained by curve tting technique and given in Table 9. Fig. 5 shows that the enhancement in compressive strength leads to higher and higher resistance to chloride penetration. From durability view, continued increase in compressive strength is benecial. Therefore, the compressive strength can be used as a roughly comparative or predictive indicator for the resistance to chloride penetration of pavement concrete. 3.3.3. Relationship between chloride permeability and pore structure of concrete To investigate the relationship between chloride permeability and pore structure of concrete, the regression analysis of data obtained by MIP and NEL is shown in Fig. 6.

616

M.-h. Zhang, H. Li / Construction and Building Materials 25 (2011) 608616 [10] Toutanji H, McNeil S, Bayasi Z. Chloride permeability and impact resistance of polypropylene-ber-reinforced silica fume concrete. Cem Concr Res 1998;28(7):9618. [11] Toutanji HA. Properties of polypropylene ber reinforced silica fume expansive-cement concrete. Constr Build Mater 1999;13:1717. [12] Vondran G, Webster T. The relationship of polypropylene ber reinforced concrete to permeability. ACI 1987(SP-108):8597. [13] Huang WH. Properties of cement-y ash grout admixture with bentonite, silica fume or organic ber. Cem Concr Res 1997;27(3):395406. [14] Oh BH, Cha SW, Jang BS, Jang SY. Development of high-performance concrete having high resistance to chloride penetration. Nucl Eng Des 2002;212:22131. [15] Li H, Zhang MH, Ou JP. Abrasion resistance of concrete containing nanoparticles for pavement. Wear 2006;260(1112):12626. [16] Li H, Zhang MH, Ou JP. Flexural fatigue performance of concrete containing nano-particles for pavement. Int J Fatigue 2007;29:1292301. [17] Li H, Xiao HG, Yuan J, Ou JP. Microstructure of cement mortar with nanoparticles. Composites Part B 2004;35:1859. [18] Li H, Xiao HG, Ou JP. A study on mechanical and pressure-sensitive properties of cement mortar with nanophase materials. Cem Concr Res 2004;34:4358. [19] Abell AB, Willis KL, Lange DA. Mercury intrusion porosimetry and image analysis of cement-based materials. J Colloid Interf Sci 1999;211: 3944. [20] Lu XY. Application of the NernstEinstein equation to concrete. Cem Concr Res 1997;27(2):293302. [21] Chen SF, Zhang DL, Zhang J, et al. The study of the road performance of the polypropylene ber concrete. Northeast Highway 2001;24(2):235 (in Chinese). [22] Lee MK, Barr BIG. An overview of the fatigue behavior of plain and bre reinforced concrete. Cem Concr Compos 2004;26:299305. [23] Ye Q, Zhang ZN, Kong DY, et al. Inuence of nano-SiO2 addition on properties of hardened cement paste as compared with silica fume. Constr Build Mater 2007;21:53945.

Acknowledgements The careful review and comments of Dr. Jinchi Lu, at the University of California, San Diego, is greatly appreciated. This study is nancially supported by NSFC with Grant No. 50908067, Postdoctoral Foundation of China and the Fundamental Research Funds for the Central Universities (DL09BB29). References
[1] Mohr P, Hansen W, Jensen E, Pane I. Transport properties of concrete pavements with excellent long-term in-service performance. Cem Concr Res 2000;30:190310. [2] Basheer L, Kropp J, Cleland DJ. Assessment of the durability of concrete from its permeation properties: a review. Constr Build Mater 2001;15:93103. [3] Alexander MG, Magee BJ. Durability performance of concrete containing condensed silica fume. Cem Concr Res 1999;29:91722. [4] Bgel L, Zivica V. Relationship between pore structure and permeability of hardened cement mortars: on the choice of effective pore structure parameter. Cem Concr Res 1997;27(8):122535. [5] Tanaka K, Kurumisawa K. Development of technique for observing pores in hardened cement paste. Cem Concr Res 2002;32:143541. [6] Peon CS, Wong YL, Lam L. The inuence of different curing conditions on the pore structure and related properties of y-ash cement pastes and mortars. Constr Build Mater 1997;11(78):38393. [7] Zhao TJ, Zhu JQ, Feng NQ. Correlation between strength and permeability of concrete. Ind Constr 1997;27(5):147 (in Chinese). [8] Wu ZW, Lian HZ. High performance concrete. Beijing: Railway Press of China; 1999. p. 43 (in Chinese). [9] Armaghani J, Larsen T, Romano D. Aspects of concrete strength and durability. Transport Res Rec 1992;1335:639.