See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/250613466

Use of nano-silica to reduce setting time and increase early strength of

concretes with high volumes of fly ash or slag

Article in Construction and Building Materials · April 2012

DOI: 10.1016/j.conbuildmat.2011.11.013

CITATIONS READS

316 603

2 authors:

Min-Hong Zhang Jahidul Islam

National University of Singapore 4 PUBLICATIONS 556 CITATIONS
138 PUBLICATIONS 6,932 CITATIONS
SEE PROFILE
SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Time-dependent chloride diffusion and chloride binding View project

All content following this page was uploaded by Min-Hong Zhang on 16 November 2019.

The user has requested enhancement of the downloaded file.

*Manuscript
Click here to view linked References

1
2
3
4 Use of Nano-Silica to Reduce Setting Time and Increase Early Strength of Concretes with
5
6 High Volumes of Fly Ash or Slag
7
8
9
10 Min-Hong Zhang a,, Jahidul Islam a
11 a
12 Department of Civil and Environmental Engineering, National University of Singapore,
13 1 Engineering Drive 2, 117576, Singapore
14 *
15 Corresponding author. Tel.: +65 65162273, fax: +65 6779 1635
16 E-mail address: [email protected] and [email protected]
17
18
19
20 Abstract
21
22 This paper presents an experimental study to evaluate the effects of nano-silica (NS) on rate
23
24
25 of cement hydration, setting time and strength development of concretes with about 50% fly ash
26
27 or slag. Results indicate that length of dormant period was shortened, and rate of cement and slag
28
29
30
hydration was accelerated with the incorporation of 1% NS in the cement pastes with high
31
32 volumes of fly ash or slag. The incorporation of 2% NS by mass of cementitious materials
33
34 reduced initial and final setting times by 90 and 100 min, and increased 3- and 7-day
35
36
37 compressive strengths of high-volume fly ash concrete by 30 and 25%, respectively, in
38
39 comparison to the reference concrete with 50% fly ash. Similar trends were observed in high-
40
41
42 volume slag concrete. Nano-silica with mean particle size of 12 nm appears to be more effective
43
44 in increasing the rate of cement hydration compared with silica fume with mean particle size of
45
46
47
150 nm.
48
49
50
51
52
53
54 Keywords: compressive strength, fly ash, heat development, nano-silica, setting time, silica
55
56 fume, slag.
57
58
59
60 1
61
62
63
64
65
 1
2
3
4 1. Introduction
5
6
7
8 Fly ash and ground granulated blast-furnace slag (GGBFS) have been used in concrete for
9
10 many years as mineral admixture to replace Portland cement partially either in batching plants or
11
12
13 in the production of blended cements. Concretes with high volumes of GGBFS have been used
14
15 for applications in marine environments and situations where ground water has high sulfate
16
17 contents. High volumes of fly ash have also been used in environments where durability is of
18
19
20 concern. Concretes with high volumes of fly ash or slag can develop good strengths over time,
21
22 exceeding those of similar concretes without fly ash or slag. However, early strengths of such
23
24
25 concretes are often lower than similar concretes without fly ash or slag which may affect
26
27 construction progress.
28
29
30
31
Recent developments in nano-technology and availability of nano-silica (NS) have made the
32
33 use of such materials in improving concrete properties possible [1-12]. Several researches show
34
35 that early-age and 28-day strengths of cement pastes [3, 4], mortars [5, 6], and concrete [7] are
36
37
38 increased by using a small amount of NS. Higher strengths of pastes [4], mortars [5, 6] and
39
40 concrete [7] with NS are also reported in comparison to those with silica fume. The higher
41
42
43 strengths are attributed to accelerated cement hydration and pozzolanic reaction [3, 4, 7], reduced
44
45 pores [5], and improved interface bonding between hardened cement paste and aggregate [3].
46
47
48 Nano-silica has also been used to increase early strength of concrete with fly ash [8, 9].
49
50
51 This paper presents an experimental study on the use of NS to improve setting time and early
52
53 strengths of mortars and concretes with high-volumes of fly ash or slag. Nano-silica with a
54
55
56 specific surface of 200.1 m2/g was used in the study in comparison to silica fume with a specific
57
58 surface area of 21.3 m2/g. As NS particles are very fine and they tend to agglomerate due to high
59
60 2
61
62
63
64
65
 1
2
3
4 surface interaction, effect of dispersion methods of NS was also investigated. In addition to the
5
6
7 compressive strength and setting time, rate of heat development of cement pastes in the first 30
8
9 hrs, and resistance to chloride-ion penetration of concretes at 28 days were studied and
10
11
12 compared. The study provides information for systematic analyses on (1) effect of NS; (2) effect
13
14 of particle sizes of reactive silica (NS vs silica fume); and (3) effect of dispersion methods on the
15
16
17 properties of fly ash and slag concretes.
18
19
20 2. Experimental details
21
22
23 In this study specimens were prepared to determine effect of NS on compressive strengths of
24
25
26 mortars (from 1 to 91 days) with about 50% ASTM C 618 class F fly ash [13] or GGBFS [14].
27
28 Silica fume was also included in the mixtures to compare with NS. A superplasticizer was used
29
30
31
to achieve target flow from 104 to 110% of the mortars. Cement pastes with the same water-to-
32
33 cementitious ratio (w/cm) and mix proportion as the mortars (except for the sand) were prepared
34
35 to determine the rate of heat development and cement hydration in the first 30 hrs. Concrete
36
37
38 mixtures were prepared to determine the effect of NS on setting times, compressive strength
39
40 development from 3 to 91 days and resistance to chloride-ion penetration at 28 days in
41
42
43 comparison to the reference concrete with 50% fly ash or slag and the concrete with silica fume.
44
45
46 2.1 Materials
47
48
49 Normal Portland Cement, ASTM C 618 Class F fly ash, and ground granulated blast-furnace
50
51
52 slag were used for cement pastes, mortars and concretes. Nano-silica1 with specific surface area
53
54 of 200.1 m2/g and average particle sizes of 12 nm were used in this study in comparison to silica
55
56
57
1
58 AEROSIL 200, Evonik Industries.
59
60 3
61
62
63
64
65
 1
2
3
4 fume which had specific surface area of 21.3 m2/g and average particle sizes of about 150 nm.
5
6
7 Silica fume used was undensified. Characteristics of these materials are given in Table 1. A
8
9 polycarboxylate based superplastisizer2 was used in mortar, paste, and concrete mixtures for
10
11
12 workability purposes. Natural sand with a fineness modulus of 2.97 was used for mortar and
13
14 concrete mixtures. Crushed granite coarse aggregate with a maximum aggregate size of 20 mm
15
16
17 was used for concrete mixtures. Both the coarse and fine aggregates met the requirements of
18
19 ASTM C 33 [15]. Tap water was used for mortar and concrete mixing, whereas deionized water
20
21
was used for cement pastes.
22
23
24
25 2.2 Mortar and concrete mixtures
26
27
28 2.2.1 Mix proportions
29
30
31
Eight mortar mixtures were included in the study (Tables 2 and 3). All the mortars had a
32
33 w/cm of 0.45 and a sand-to-cementitious materials ratio of 2.75. Mortars with 1% NS were
34
35 compared to that with the same amount of silica fume to evaluate the effect of specific surface
36
37
38 area and particle size of silica (Table 2). As the NS particles were extremely fine, influences of
39
40 mixing and dispersing methods on properties of the mortars were also evaluated (Table 3). In
41
42
43 addition to the mortars, effect of 2% NS on concrete properties was studied in comparison to that
44
45 of silica fume. Mix proportions of the concretes are given in Table 4.
46
47
48
2.2.2 Specimen preparation, curing, and testing
49
50
51 2.2.2.1 Mortars
52
53
54
55
56
57
2
58 ADVA 181N, W.R. Grace (Singapore) Pte. Ltd.
59
60 4
61
62
63
64
65
 1
2
3
4 Mortars were mixed in a Hobart mixer at an ambient temperature of about 30 oC. For mortar
5
6
7 mixtures with mechanical mixing, solid materials were dry mixed first. Water was added and
8
9 mixed for 1 min followed by addition of superplasticizer and mixed for 1 more min at low speed
10
11
12 and 30 seconds at high speed. The flow value was determined according to ASTM C 1437 [16].
13
14
15 For ultrasonic mixing, nano-silica and water were mixed first using ultrasonic mixer with 90
16
17 Watts power input for 5 minutes. The sonicated mixture was then mixed in a Hobart mixer with
18
19
20 sand, cement and fly ash or slag for 1 min. After that, superplasticizer was added and mixed for 1
21
22 min at low speed and 30 seconds at high speed.
23
24
25
26 For each mortar mixture, fifteen 50x50x50-mm specimens were cast for compressive strength
27
28 test. The molded specimens were covered with wet burlap for the first 24 hours to prevent
29
30
31
moisture loss. After demold, the specimens were cured in a fog room at a temperature of about
32
33 28 - 30 oC until the time of testing. Compressive strengths of the mortars were determined at 1,
34
35 3, 7, 28, and 91 days according to ASTM C 109/C 109M [17].
36
37
38
39 2.2.2.2 Concretes
40
41 Concretes were mixed using a pan mixer at an ambient temperature of about 30 ºC. Before
42
43
44 concrete mixing, NS or silica fume were mixed with water using the ultrasonic mixer for
45
46 dispersion of the particles. The sonicated mixture was then mixed with aggregate, cement, and
47
48
fly ash or slag in a pan mixer for 1 min. The superplasticizer was added last and mixed for
49
50
51 another 1-2 minutes to achieve a target slump of about 100 mm.
52
53
54 Twelve 100-mm cubes and one 100x200-mm cylinders were cast for each concrete mixture
55
56
57 for determining compressive strength and chloride-ion penetrability, respectively. Mortar sieved
58
59
60 5
61
62
63
64
65
 1
2
3
4 from the concrete was used to cast a 150-mm cube to determine setting time of concrete.
5
6
7 Compressive strengths of concretes were determined at 3, 7, 28, and 91 days according to BS EN
8
9 12390-3 [18], setting time of concretes were determined according to ASTM C 403/C 403M
10
11
12 [19], and resistances to chloride-ion penetration were determined at 28 days according to ASTM
13
14 C 1202 [20]. Curing of the concretes was the same as that of the mortar specimens.
15
16
17
2.3 Cement paste mixtures
18
19
20
21 2.3.1 Mix proportions and mixing
22
23 Mix proportions of cement pastes were similar to those of the mortars except for the exclusion
24
25
26 of sand. For ultrasonic mixing, NS and water were premixed in ultrasonic machine for dispersion
27
28 of fine particles. Before paste mixing, all the materials including sonicated mixtures were pre-
29
30
31
conditioned at 30 °C for 24 hours. The mixing procedures for cement pastes were similar to
32
33 those of the mortars.
34
35
36 2.3.2 Evaluate the rate of heat generation and cement hydration
37
38
39 Effect of NS on the rate of heat generation in cement pastes was evaluated according to
40
41 ASTM C 1679 [21] by a Thermometric TAM Air 3115 isothermal calorimeter at a temperature
42
43
44 of 30 °C. This temperature was selected to simulate weather conditions in tropical countries. The
45
46 heat generation in the cement pastes reflects rate of cement hydration. The calorimeter was
47
48
conditioned at 30 °C for a day before experiments, and amplifier range was set at 600 mW.
49
50
51
52 After the mixing, paste sample of about 10 grams was transferred into a sample ampoule with
53
54 the sample mass recorded. After capping the ampoule, the sample and reference ampoules were
55
56
57 inserted into the calorimeter. The calorimeter started to record heat at about 15 minutes after the
58
59
60 6
61
62
63
64
65
 1
2
3
4 cementitious materials were in contact with water, thus the heat generated initially during mixing
5
6
7 and preparation was not captured. The heat generated from the cement hydration was monitored
8
9 continuously for 30 hours. The power output (in mili-watt) from the calorimeter due to the heat
10
11
12 generated was recorded every minute. The power output was normalized based on sample mass.
13
14 The normalized power output was then converted to heat generated in the sample (in
15
16
17 joules/gram).
18
19
20 3. Results and discussion
21
22
23 3.1 Rate of heat development
24
25
26
27
3.1.1 Effect of nano-silica
28
29 Figures 1 and 2 show effect of NS or silica fume on rate of heat development of the high-
30
31 volume fly ash and slag cement pastes, respectively, in comparison to corresponding reference
32
33
34 pastes with 50% fly ash or slag. With the incorporation of 1% NS or silica fume, length of
35
36 dormant period was reduced, and Peak 2 and Peak 3 of the fly ash and slag cement pastes shifted
37
38
39 to left. The Peak 3 of the fly ash cement paste with the NS also increased in magnitude. The
40
41 incorporation of the NS, however, shortened the dormant period and increased the rate of heat
42
43
44 development and cement hydration of the pastes more significantly than the silica fume. S ilica
45
46 fume did not affect the Peak 3 of the fly ash cement paste significantly. At 24 hrs total cumulative
47
48
heat was increased in the pastes with NS and silica fume. However, total cumulative heat was
49
50
51 higher in the pastes with the NS than those with silica fume.
52
53
54 It was observed that calorimeter curves for the fly ash and slag cement pastes were different.
55
56
57 In the fly ash pastes, Peak 2 occurred at about 10 hrs, whereas Peak 3 occurred before 15 hrs
58
59
60 7
61
62
63
64
65
 1
2
3
4 (Fig. 1). As Class F fly ash generally has limited reactivity at early stage, Peaks 2 and 3 of the fly
5
6
7 ash cement pastes are likely corresponded to C3S hydration and C3A reaction, respectively,
8
9 similar to hydration features observed in typical Portland cement paste [22]. For the slag cement
10
11
12 pastes, Peak 2 also occurred at about 10 hrs but Peak 3 occurred at about 18 to 20 hrs (Fig. 2).
13
14 The Peaks 2 and 3 are likely corresponded to Portland cement hydration and slag hydration,
15
16
17 respectively, according to ACI Committee 233 Report [23].
18
19
20 Shift of the Peak 2 to left and shortening of the dormant period in the calorimeter curves of
21
22 the fly ash pastes (Fig. 1) might be related to accelerated hydration of C3S due to increased
23
24
25 nucleation sites provided by the fine NS. In a study on the effect of NS on the hydration of
26
27 calcium silicate C3S, Stein and Stevels [24] found out that the NS accelerates the hydration rate
28
29
30 of C3S. The acceleration is explained by increased conversion rate from a protective hydrate
31
32 layer into a less protective one due to the incorporation of NS which reduced calcium and
33
34
35
hydroxyl concentration during the first minute of the hydration in the paste. They envisage more
36
37 ettringite precipitation far from C3A surface as a result of the lower calcium concentration in
38
39 paste with NS at early stage. This probably enabled accelerated reaction of the C3A and earlier
40
41
42 depletion of SO3 [25] in the system and shifted the Peak 3 to left in the paste with NS as shown
43
44 in Fig. 1.
45
46
47
48 For the slag pastes (Fig. 2), shift of the Peaks 2 and 3 to the left in the calorimeter curves
49
50 corresponded to accelerated hydration of Portland cement and accelerated slag reaction,
51
52 respectively. The accelerated cement hydration might be due to increased nucleation sites
53
54
55 provided by the fine NS particles. In addition to the effect of fine particle size of the NS and
56
57 silica fume, the accelerated slag hydration (Peak 3) might be attributed to increased
58
59
60 8
61
62
63
64
65
 1
2
3
4 concentration of calcium hydroxide in solution due to increased C3S reaction. However, the
5
6
7 changes of the Peaks 2 and 3, and dormant period were not significant for the slag pastes with
8
9 NS due to effect of retardation when higher dosage of superplasticizer was used to achieve a
10
11
12 given workability (Table 2).
13
14
15 It was observed that at 24 hrs the increase in the cumulative heat of the fly ash paste with NS
16
17 was more significant (20%) than that of the slag paste (6.5%) in comparison to the corresponding
18
19
20 reference paste. These results are consistent with 1-day strength increases (will be discussed
21
22 later) of fly ash and slag mortars shown in Table 6.
23
24
25
26 3.1.2 Effect of mixing and dispersion method
27
28 Figures 3 and 4 show effect of mixing and dispersion method of NS on the rate of heat
29
30
31
development of fly ash and slag cement pastes, respectively, and the corresponding cumulative
32
33 heat development is shown in the inset. For both fly ash and slag pastes with NS premixed with
34
35 water using an ultrasonic equipment, the dormant period was reduced and both Peaks 2 and 3
36
37
38 shifted left and occurred before those of the corresponding reference fly ash or slag paste. For the
39
40 fly ash paste prepared by mechanical mixing (Fig. 3), Peaks 2 and 3 are also shifted to left.
41
42
43 Comparing the fly ash pastes prepared by the two different methods, the extent of the shift and
44
45 increase in the magnitude of the Peaks 2 and 3 were more significant by using ultrasonicated NS
46
47
48 than mechanical mixing method. For the slag paste prepared by mechanical mixing, however, the
49
50 length of dormant period was increased, and Peaks 2 and 3 were shifted to right than those of the
51
52
reference slag paste (Fig. 4).
53
54
55
56 The phenomena observed for the paste by mechanical mixing might be related to less
57
58 homogeneous dispersion of NS in both slag and fly ash pastes as well as retarding effect due to
59
60 9
61
62
63
64
65
 1
2
3
4 higher dosage of superplasticizer used in the slag cement paste (Table 3) to achieve a given
5
6
7 workability. The NS particles are extremely small and likely agglomerate due to high surface
8
9 interaction. The agglomerated NS will reduce nucleation sites for precipitation of hydration
10
11
12 products, thus reduce the rate of reactions.
13
14
15 Cumulative heat generated within the first 24 hrs in the fly ash and slag cement pastes with
16
17 ultrasonicated NS was higher than that with NS mechanically mixed with other ingredients
18
19
20 which suggests that the cement and slag hydration was increased by the sonication of NS and
21
22 water.
23
24
25
26 3.2 Setting time of concretes
27
28
29 Effects of 2% NS on the initial and final setting times of high-volume fly ash and slag
30
31 concretes in comparison to corresponding reference concretes and concretes with 2% silica fume
32
33
34 are shown in Table 5. Significant reductions of the initial and final setting times were observed
35
36 for both the fly ash and slag concretes with 2% NS. The incorporation of 2% NS reduced the
37
38
39 initial and final setting times of the fly ash concrete by 90 min and 100 min, respectively. In the
40
41 slag concrete, incorporation of the same amount NS reduced the initial and final setting times by
42
43
44 95 min and 105 min, respectively. However, the incorporation of 2% silica fume did not affect
45
46 the setting times of the fly ash and slag concretes significantly.
47
48
49 3.3 Compressive strength development
50
51
52
53 3.3.1 Effect of nano-silica on strength development of high-volume fly ash or slag mortars
54
55 The effects of NS on compressive strength developments of the high-volume fly ash and slag
56
57
58
mortars compared to those with silica fume are shown in Table 6. The compressive strengths of
59
60 10
61
62
63
64
65
 1
2
3
4 the fly ash and slag mortars were generally increased with the incorporation of 1% NS or silica
5
6
7 fume in comparison to the corresponding reference mortars with 50% fly ash or slag.
8
9
10 The NS showed more significant effect on the strength development than the silica fume,
11
12
13 especially at early ages. For example, the strengths of the fly ash mortars with 1% NS were
14
15 increased by 61 and 25% at 1 and 3 days, respectively, whereas those with 1% silica fume were
16
17 increased by 13 and 15% compared to those of the reference fly ash mortars. The results are
18
19
20 consistent with findings by Qing et al. [3]. It is noted that the incorporation of the NS had less
21
22 significant effect on the 1-day strength of the slag mortars than at 3 and 7 days. This might be
23
24
25 related to the higher dosages of the superplasticizer used which had retarding effect in the
26
27 mortars with NS to achieve a given workability.
28
29
30
31
In terms of percentage of strength increase, the NS and silica fume seems to have similar
32
33 effect on the fly ash and slag mortars at 3 and 7 days, but less effect on fly ash mortars at 28 and
34
35 91 days compared with the slag mortars. At the age of 1 day, 1% NS increased the strength of the
36
37
38 fly ash mortar by 61% from 7.4 to 12.0 MPa, whereas 1% NS increased the strength of slag
39
40 mortar by only 18%. The difference may be attributed to the characteristic difference between fly
41
42
43 ash and slag. When mixed with water, slag can hydrate under the activation of cement and lime,
44
45 whereas Class F fly ash is pozzolanic material and has limited reactivity at early age. Thus, early
46
47
48 strength of slag mortar is higher than that of fly ash mortar with given volume of the slag or fly
49
50 ash. Due to accelerated heat development shown in the calorimeter curve and possibility of
51
52 acceleration of C3S and C3A reactions, the NS appears to have more effect on 1-day strength of
53
54
55 the fly ash mortar than on the slag mortar.
56
57
58
59
60 11
61
62
63
64
65
 1
2
3
4 3.3.2 Effect of mixing and dispersion method on strength development of mortars
5
6
7 The effect of mixing and dispersion methods of NS on compressive strength developments of
8
9 the fly ash and slag mortars are shown in Table 7. The compressive strengths were higher for fly
10
11
12 ash mortars prepared by the sonication of NS than those of mechanical mixing method.
13
14 However, no significant difference was observed in strength development of the slag mortars
15
16
17 prepared by ultrasonicated NS with water and mechanical mixing method. This difference might
18
19 be attributed to the lower density of the slag mortar SL11 than that of the mortar SL11 (M).
20
21 Careful examination of the data shows that the density of the mortar prepared by ultra-sonication
22
23
24 of nano-silica (2231kg/m3) was lower than that prepared by mechanical mixing (2275 kg/m3).
25
26 The difference on the density of the mortars might have affected the strength. The lower density
27
28
29 of the mortar prepared by the ultrasonication of nano-silica (SL11) might have resulted in lower
30
31 compressive strength. This suggests that if the density of the two mixtures SL11 and SL11(M)
32
33
34 was the same, the former might have higher strength than the latter, consistent with the heat and
35
36 rate of cement and slag hydration as discussed in the section 3.1.2. The lower density of the
37
38
39
mortar SL11 might be due to inadequate consolidation. The results indicate that ultrasonication
40
41 of NS with water is probably a better method to disperse the NS particles properly in comparison
42
43 to the mechanical mixing. However, further research is needed to confirm this.
44
45
46
47 3.3.3 Strength development of high-volume slag or fly ash concrete with nano-silica
48
49 Compressive strength development of fly ash and slag concretes with 2% NS or silica fume in
50
51
52 comparison to that of the reference fly ash and slag concretes is presented in Table 5. The
53
54 compressive strengths of the fly ash and slag concretes were increased with the incorporation of
55
56 the NS in comparison to the corresponding reference concretes, especially at early ages.
57
58
59 However, silica fume did not show significant effect on the strengths of the fly ash and slag
60 12
61
62
63
64
65
 1
2
3
4 concretes. For example, with the incorporation of NS, the compressive strengths of the fly ash
5
6
7 concrete were increased by 30 and 25% at 3 and 7 days, respectively, whereas those with silica
8
9 fume were increased by only 5 and 6%, respectively, compared to the reference fly ash concrete.
10
11
12 Similar trends of strength increase due to the NS and silica fume were observed for the slag
13
14 concrete at early ages as well.
15
16
17 Comparing the fly ash and slag concretes, the NS and silica fume did not show significant
18
19
20 effect on the slag concrete at 28 and 91 days, whereas the NS increased fly ash concrete by 13%
21
22 and 18% at 28 and 91 days, respectively, in comparison with the reference fly ash concrete. This
23
24
25 might be attributed to the coarse aggregate used which appears to have reached its strength limit
26
27 at about 70 MPa in the slag concretes.
28
29
30
31
In ordinary concrete, interface transition zone (ITZ) between the coarse aggregate and mortar
32
33 matrix is usually the weakest link. As a result, cracks generally go through the ITZ around coarse
34
35 aggregate particles. With reduction of w/cm and use of fine mineral admixture such as NS or
36
37
38 silica fume, the ITZ and mortar matrix can be improved substantially. Thus, the strength of the
39
40 concrete can be improved. However, if the strengths of the ITZ and mortar matrix are improved
41
42
43 to such extents that coarse aggregate becomes the weakest link in concrete, crack will go through
44
45 the coarse aggregate particles. In such conditions, reducing w/cm and using fine mineral
46
47
48 mixtures will no longer increase the concrete strength because coarse aggregate is a limiting
49
50 factor for the strength of concrete. Figure 5 shows that cracks went through coarse aggregate
51
52 particles in the slag concrete with 2% NS after a compression test. This might explain why the
53
54
55 strength of the slag concrete with 2% NS was not increased further at 28 and 91 days.
56
57
58
59
60 13
61
62
63
64
65
 1
2
3
4 3.4 Effect of nano-silica on resistance to chloride-ion penetration
5
6
7
8 Information on the chloride-ion penetrability of the high-volume fly ash and slag concretes
9
10 with 2% NS or silica fume in comparison to that of the reference concretes is presented in Table
11
12
13 5. The results show that the total charge passed through the fly ash and slag concretes with the
14
15 NS or silica fume was lower than that of the corresponding reference concretes. However,
16
17 differences on the charge passed through the concretes with NS or silica fume were not
18
19
20 significant. The concretes with NS or silica fume had charges passed below 1000 coulombs,
21
22 which is considered “very low” according to ASTM C 1202 [20].
23
24
25
26 3.5 Discussion
27
28
29 Both the NS and silica fume are nano-sized highly reactive silica, but the average primary
30
31 particle size of the former is about 10 times smaller than that of the latter. The mechanisms by
32
33
34 which silica fume modifies cement paste, mortar, and concrete are summarized in ACI
35
36 Committee 234 report [26]. These mechanisms are also applicable to NS. As the particle sizes of
37
38
39 the NS are much smaller than those of the silica fume, the physical and chemical effect of the
40
41 former is likely more substantial than the latter. Their effects on setting time, early strength
42
43
44 development and resistance to chloride penetration of the high-volume fly ash and slag concretes
45
46 will be discussed below.
47
48
49 3.5.1 Physical effect
50
51
52 From physical perspective, extremely fine particle size of the NS may have accelerated
53
54 cement and slag hydration by providing high amount of nucleation sites for precipitation of
55
56
57 cement hydration products in the high-volume fly ash and slag concretes. In the slag concrete,
58
59
60 14
61
62
63
64
65
 1
2
3
4 the accelerated cement hydration also results in increased amount of calcium hydroxide in
5
6
7 solution which activates and speeds up slag hydration.
8
9
10 In addition to nucleation effect, NS may have acted as reactive filler which reduces bleeding
11
12
13 and increases packing density of solid materials by occupying space between cement, fly ash,
14
15 and slag particles. These physical effects of the NS may have contributed to the reduced setting
16
17 time and increase early strength of the fly ash and slag concretes observed. However, as both the
18
19
20 NS and silica fume are finer than Portland cement, fly ash, and slag, the filler effect of the NS
21
22 and silica fume may be similar.
23
24
25
26 3.5.2 Chemical effect
27
28 From chemical point of view, NS is highly reactive pozzolanic material and reacts with
29
30
31
calcium hydroxide (CH) from cement hydration to form calcium silicate hydrates (CSH). Zhang
32
33 and Gjørv [27] reported pozzolanic reaction of silica fume as early as 1-day of cement hydration.
34
35 Since the NS had specific surface area about 10 times higher than that of silica fume, the
36
37
38 pozzolanic reaction of the NS might have started before 24 hrs. The pozzolanic reaction of the
39
40 NS at very early age might have also contributed to the reduced setting times and increase early
41
42
43 strength of the fly ash and slag concretes observed.
44
45
46 3.5.3 Microstructure modification
47
48
In terms of microstructure modifications, the NS might reduce porosity in cement paste and in
49
50
51 ITZ between the cement paste and aggregate due to the physical and chemical effects discussed
52
53 above. It is also reported that NS can reduce CH crystal size in the ITZ more effectively than
54
55
56 silica fume [28]. The above effects increased the density of the cement paste and improved
57
58
59
60 15
61
62
63
64
65
 1
2
3
4 bonding between the cement paste and aggregate which might have contributed to the strength
5
6
7 development and reduced chloride penetrability of the concretes.
8
9
10 4. Conclusions
11
12
13
Based on the experimental results using nano-silica in pastes, mortars, and concretes with
14
15
16 about 50% of fly ash or slag at w/cm of 0.45, following conclusions can be drawn:
17
18
19 1. Length of dormant period was shortened, and rate of cement and slag hydration was
20
21
22 accelerated with the incorporation of 1% NS in the cement pastes with high volumes of fly ash or
23
24 slag.
25
26
27 2. The incorporation of 2% NS by mass of cementitious materials reduced initial and final setting
28
29
30 times by 90 and 100 min, and increased 3- and 7-day compressive strengths of high-volume fly
31
32 ash concrete by 30 and 25%, respectively, in comparison to the reference concrete with 50% fly
33
34
35 ash. Similar trends were observed in high-volume slag concrete.
36
37
38 3. At 28 and 91 days, the NS increased strength of fly ash concrete compared to the reference fly
39
40
ash concrete. However, the NS did not increase the strengths of the slag concrete at these ages,
41
42
43 which might be related to the coarse aggregate used which appears to have reached its strength
44
45 limit.
46
47
48
49 4. Nano-silica with mean particle size of 12 nm appears to be more effective in increasing the
50
51 rate of cement hydration compared with silica fume with mean particle size of 150 nm. The NS
52
53
54
reduced the setting times and increased early strengths of the high-volume fly ash or slag
55
56 concrete. However, the setting times and early strength of these concretes were not affected by
57
58 the silica fume significantly.
59
60 16
61
62
63
64
65
 1
2
3
4 5. The 28-day charges passed through the fly ash or slag concretes with 2% NS or silica fume
5
6
7 were similar, and were lower than those of the corresponding reference concretes.
8
9
10 Acknowledgements
11
12
13
Grateful acknowledgement is made to National University of Singapore for providing partial
14
15
16 scholarship to the second author. Appreciation is made to past undergraduate student Huynh
17
18 Thanh Binh, Structure Laboratory Technologist Ang Beng Oon, and Research Fellow Li Wei
19
20
21 who contributed to some of the experimental work.
22
23
24 References
25
26
27 [1] Sobolev K, Gutierrez MF. How nanotechnology can change the concrete world. American
28 Ceramic Society Bulletin. 2005;84(10):14-7.
29
30 [2] Sanchez F, Sobolev K. Nanotechnology in concrete - A review. Construction and Building
31
32
Materials. 2010;24(11):2060-71.
33
34 [3] Qing Y, Zenan Z, Deyu K, Rongshen C. Influence of nano-SiO2 addition on properties of
35 hardened cement paste as compared with silica fume. Construction and Building Materials.
36 2007;21(3):539-45.
37
38
39
[4] Porro A, Dolado JS, Campillo I, Erkizia E, Miguel Yd, Ibarra YSd. Effects of nanosilica
40 additions on cement pastes. In: Dhir RK, Newlands MD, Csetenyi LJ, editors. Applications of
41 nanotechnology in concrete design. London: Thomas Telford; 2005. p. 87-96.
42
43 [5] Li H, Xiao H-G, Yuan J, Ou J. Microstructure of cement mortar with nano-particles.
44 Composites Part B: Engineering. 2004;35(2):185-9.
45
46
47 [6] Jo B-W, Kim C-H, Tae G-h, Park J-B. Characteristics of cement mortar with nano-SiO2
48 particles. Construction and Building Materials. 2007;21(6):1351-5.
49
50 [7] Schoepfer J, Maji A. An investigation into the effect of silicon dioxide particle size on the
51 strength of concrete. ACI Special Publication. 2009;267(5):45-58.
52
53
54 [8] Li G. Properties of high-volume fly ash concrete incorporating nano-SiO2. Cement and
55 Concrete Research. 2004;34(6):1043-9.
56
57 [9] Said AM, Zeidan MS. Enhancing the reactivity of normal and fly ash concrete using colloidal
58 nano-silica. ACI Special Publication. 2009;267(7):75-86.
59
60 17
61
62
63
64
65
 1
2
3
4 [10] Collepardi M, Ogoumah-Olagot JJ, Skarp U, Troli R. Influence of amorphous colloidal
5
6 silica on the properties of self-compacting concretes. In: Proceedings of the International
7 Conference, Challenges in Concrete Construction - Innovations and Developments in Concrete
8 Materials and Construction, Dundee, UK; 2002. p. 473 - 83.
9
10 [11] Björnström J, Martinelli A, Matic A, Börjesson L, Panas I. Accelerating effects of colloidal
11
12
nano-silica for beneficial calcium-silicate-hydrate formation in cement. Chemical Physics
13 Letters. 2004;392(1-3):242-8.
14
15 [12] Flores I, Sobolev K, Torres-Martinez L, Cuellar E, Valdez P, Zarazua E. Performance of
16 cement systems with nano-SiO2 particles produced by using the sol-gel method. Transportation
17
Research Record: Journal of the Transportation Research Board. 2010;2141:10-4.
18
19
20 [13] ASTM C 618. Standard specification for coal fly ash and raw or dalcined natural pozzolan
21 for use in concrete. Annual Book of ASTM Standards, vol. 04.02; 2008.
22
23 [14] ASTM C 989. Standard specification for slag cement for use in concrete and mortars.
24
Annual Book of ASTM Standards, vol. 04.02; 2010.
25
26
27 [15] ASTM C 33. Standard specification for concrete aggregates. Annual Book of ASTM
28 Standards, vol. 04.02; 2008.
29
30 [16] ASTM C 1437. Standard test method for flow of hydraulic cement mortar. Annual Book of
31
ASTM Standards, vol. 04.01; 2005.
32
33
34 [17] ASTM C 109/C 109M. Standard test method for compressive strength of hydraulic cement
35 mortars (using 2-in or [50-mm] cube specimens). Annual Book of ASTM Standards, vol. 04.01;
36 2005.
37
38 [18] BS EN 12390-3. Testing hardened concrete - part 3: compressive strength of test specimens.
39
40 British Standards Institution; 2002.
41
42 [19] ASTM C 403/C 403M. Standard test method for time of setting of concrete mixtures by
43 penetration resistance. Annual Book of ASTM Standards, vol. 04.02; 2008.
44
45 [20] ASTM C 1202. Standard test method for electrical indication of concrete’s ability to resist
46
47 chloride ion penetration. Annual Book of ASTM Standards, vol. 04.02; 2008.
48
49 [21] ASTM C 1679. Practice for measuring hydration kinetics of hydraulic cementitious
50 mixtures using isothermal calorimetry. Annual Book of ASTM Standards, vol. 04.02; 2008.
51
52 [22] Mindess S, Young JF, Darwin D. Concrete. 2nd ed. Upper Saddle River, NJ: Prentice Hall;
53
54 2003.
55
56 [23] ACI Committee 233. Slag cement in concrete and mortar, ACI 233R-03, American
57 Concrete Institute; 2003.
58
59
60 18
61
62
63
64
65
 1
2
3
4 [24] Stein HN, Stevels JM. Influence of silica on the hydration of 3CaO,SiO2. Journal of Applied
5
6 Chemistry. 1964;14(8):338-46.
7
8 [25] Buil M, Paillère AM, Roussel B. High strength mortars containing condensed silica fume.
9 Cement and Concrete Research. 1984;14(5):693-704.
10
11 [26] ACI Committee 234. Guide for the use of silica fume in concrete, ACI 234R-06, American
12
13 Concrete Institute; 2006.
14
15 [27] Zhang M-H, Gjørv OE. Effect of silica fume on cement hydration in low porosity cement
16 pastes. Cement and Concrete Research. 1991;21(5):800-8.
17
18 [28] Qing Y, Zenan Z, Li S, Rongshen C. A comparative study on the pozzolanic activity
19
20 between nano-SiO2 and silica fume. Journal of Wuhan University of Technology--Materials
21 Science Edition. 2006;21(3):153-7.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 19
61
62
63
64
65
Table

Table 1 Physical properties and chemical compositions of materials

Portland Silica Nano-

Fly ash Slag
cement fume silica

CaO 63.4 3.9 41.8 0.2 --

SiO2 20.1 46.3 33.1 95.9 >99.8*
Al2O3 4.1 28.5 13.7 0.3 --
Fe2O3 3.3 18.5 0.7 0.3 --
Chemical
MgO 3.6 1.8 4.9 0.4 --
composition, %
Na2O 0.2 0.2 0.2 0.05 --
K2O 0.4 0.6 0.5 0.6 --
SO3 2.1 0.2 0.7 0.2 --
LOI 2.4 2.3 0.6 1.5 --
C3S 66.8 -- -- -- --
Mineral C2S 7.3 -- -- -- --
phases, % C3A 5.3 -- -- -- --
C4AF 10.1 -- -- -- --
Blain fineness, m2/kg 308 -- -- -- --
2
Physical BET surface area,m /g -- -- -- 21.3 200.1
properties, % Average primary particle size 28.2μm 27.3μm 16.7μm 150nm* 12nm*
Specific gravity 3.15 2.47 2.94 2.2* 2.2*
* Information provided by supplier

Table 2 Mix proportions to compare the effect of nano-silica in fly ash and slag mortars in
comparison to that of silica fume (w/cm = 0.45)

Mix proportion
Mixing Flow,
Mix ID Fly Nano- Silica Super-
procedure Water Cement Slag Sand %
ash silica fume plasticizer**
FA0 Mechanical 0.45 0.5 0.5 0 0 0 2.75 0.21 107
FA11 * 0.45 0.5 0.49 0 0.01 0 2.75 0.71 108
FA1SF Mechanical 0.45 0.5 0.49 0 0 0.01 2.75 0.28 106
SL0 Mechanical 0.45 0.5 0 0.5 0 0 2.75 0.42 110
SL11 * 0.45 0.5 0 0.49 0.01 0 2.75 0.88 110
SL1SF Mechanical 0.45 0.5 0 0.49 0 0.01 2.75 0.42 107
* With ultrasonic premixing of nano-silica + water
** % of (cement + fly ash or slag + nano-silica or silica fume)
Table 3 Mix proportions of mortars for evaluating mixing and dispersion methods of nano-silica
(w/cm = 0.45)

Mixing and Mix proportion

Flow,
Mix ID dispersing Fly Nano- Super-
Water Cement Slag Sand %
procedure ash silica plasticizer**
FA11 * 0.45 0.5 0.49 0 0.01 2.75 0.71 108
FA11 (M) Mechanical 0.45 0.5 0.49 0 0.01 2.75 0.57 108
SL11 * 0.45 0.5 0 0.49 0.01 2.75 0.88 110
SL11 (M) Mechanical 0.45 0.5 0 0.49 0.01 2.75 1.17 104
* With ultrasonic premixing of nano-silica + water
** % of (cement + fly ash or slag + nano-silica) by mass,

Table 4 Mix proportions to compare the effect of nano-silica in fly ash and slag concrete in
comparison to that of silica fume (w/cm = 0.45)

Mix proportion, kg/m3

Mixing Slump,
Mix ID Fly Nano- Silica Super-
procedure Cement Slag CA Sand mm
ash silica fume plasticizer
CFA0 Mechanical 200 200 -- 0 0 1014 740 0.5 110
CFA21 * 200 192 -- 8 0 1014 739 3.4 100
CFA2SF * 200 192 -- 0 8 1014 739 0.6 105
CSL0 Mechanical 200 -- 200 0 0 1014 774 1.4 95
CSL21 * 200 -- 192 8 0 1014 771 4.0 85
CSL2SF * 200 -- 192 0 8 1014 771 1.7 85
* With ultrasonic premixing of nano-silica or silica fume with water

Table 5 Effect of nano-silica on setting time, compressive strength, and charge passed in the fly
ash and slag concretes in comparison to that of silica fume (w/cm = 0.45)

Mixing and Setting time, Charge

Compressive strength, MPa
Mix ID dispersing Binder type hr:min passed,
procedure Initial Final 3-day 7-day 28-day 91-day Coulomb
50% fly ash,
CFA0 Mechanical 6:05 8:15 19.5 28.1 43.0 50.2 1154
50% cement
2% NS,
CFA21 * 48% fly ash, 4:35 6:35 25.3 35.0 48.7 59.3 858
50% cement
2% silica fume,
CFA2SF * 48% fly ash, 5:45 8:05 20.4 29.9 43.5 51.9 891
50% cement
50% slag,
CSL0 Mechanical 6:05 8:10 35.4 48.1 68.0 69.3 1049
50% cement
2% NS,
CSL21 * 48% slag, 4:30 6:25 43.1 56.8 69.8 71.1 786
50% cement
2% silica fume,
CSL2SF * 48% slag, 5:50 8:05 36.7 50.5 68.4 69.7 946
50% cement
* With ultrasonic premixing of nano-silica or silica fume with water

Table 6 Effect of nano-silica on the compressive strength of fly ash and slag mortars in
comparison to that of silica fume (w/cm = 0.45)

Compressive strength, MPa

Mix ID Binder type
1-day 3-day 7-day 28-day 91-day
50% fly ash,
FA0 7.4 18.1 26.9 40.8 48.3
50% cement
1% NS, 49% fly ash,
FA11 12.0 22.5 31.5 43.6 50.4
50% cement
1% silica fume, 49% slag,
FA1SF 8.4 20.8 29.7 42.3 48.9
50% cement
50% slag,
SL0 13.8 27.3 40.4 53.8 55.9
50% cement
1% NS, 49% slag,
SL11 16.3 35.8 47.0 60.2 64.3
50% cement
1% silica fume, 49% slag,
SL1SF 15.2 32.1 46.1 59.8 63.0
50% cement

Table 7 Effect of mixing and dispersion methods of nano-silica on the compressive strength of
mortars (w/cm = 0.45)

Mixing and Compressive strength, MPa

Mix ID dispersing Binder type
procedure 1-day 3-day 7-day 28-day 91-day
50% fly ash,
FA0 Mechanical 7.4 18.1 26.9 40.8 48.3
50% cement
FA11 * 1% NS, 12.0 22.5 31.5 43.6 50.4
49% fly ash,
FA11 (M) Mechanical 50% cement 9.8 20.3 30.0 41.1 49.3
50% slag,
SL0 Mechanical 13.8 27.3 40.4 53.8 55.9
50% cement
SL11 * 1% NS, 16.3 35.8 47.0 60.2 64.3
49% slag,
SL11 (M) Mechanical 50% cement 15.9 35.7 47.3 59.3 63.5

* With ultrasonic premixing of nano-silica + water

Figure

Fig. 1. Effect of nano-silica or silica fume on the rate of heat development in fly ash cement
paste (nano-silica and silica fume contents are 1% of cementitious materials by mass)
Figure

Fig. 2. Effect of nano-silica or silica fume on the rate of heat development in slag cement paste
(nano-silica and silica fume contents are 1% of cementitious materials by mass)
Figure

Fig. 3. Effect of mixing and dispersing method on the rate of heat development in fly ash cement
paste with 1% nano-silica
Figure

Fig. 4. Effect of mixing and dispersing method on the rate of heat development in slag cement
paste with 1% nano-silica
Figure

Fig. 5. Crack pattern in slag concrete with 2% nano-silica under compressive load. Crack goes
through coarse aggregate particles

View publication stats