Beruflich Dokumente
Kultur Dokumente
A R T I C L E I N F O A B S T R A C T
Keywords: This study aims to clarify the role of micro silica in hydration of UHPC. The behavior of two different types of
UHPC micro silica in UHPC was investigated with regard to their filler effect and pozzolanic reaction by using ana-
Micro silica lytical techniques; XRD, TG, 29Si and 27Al NMR spectroscopy, and MIP. The micro silica with high pozzolanic
Hydration product activity led to the higher level of Al-substitution for Si in C-S-H and the denser structure, thus increasing
Microstructure
compressive strength, whereas that facilitating filler effect limited the consumption of Ca(OH)2 even after high
Filler effect
temperature curing and led to the higher amount of AFm phase. In the UHPC showing high filler effect, addi-
tional hydration of C3S and C2S occurred at later ages, increasing the fraction of Q1 site in C-S-H and decreasing
the porosity in the pore diameter region below 10 nm. Consequently, a significant increase in the compressive
strength of this UHPC was achieved.
1. Introduction pozzolanic reaction in which the incorporated micro silica reacts with
portlandite (Ca(OH)2, CH) resulted from the hydration of alite [4,5,50].
Ultra-high performance concrete (UHPC) was recently defined as a Second, the particle size of amorphous silica ranging in sub-micro-
cement-based composite with a compressive strength exceeding meters is effective for filling the voids present among cement particles
150 MPa [1]. UHPC is typically fabricated using cement, water, micro and other constituent materials, termed as filler effect [4].
silica, filler and fine aggregate as well as superplasticizer. The most Cement matrix is significantly densified by the filler effect, since the
distinctive properties of UHPC are extremely low porosity and high voids present in the matrix can be filled with undissolved silica particles
packing density, resulting from particles with widely distributed dia- [6,7]. Another principle of filler effect is that nucleation of calcium
meters ranging from 0.1 to 1000 μm and a water-to-cement (w/c) ratio silicate hydrate (C-S-H) phases which are formed from alite hydration
as low as 0.20. The key feature in the material design of UHPC is the use occurs on the surface of filler materials [2,8]; this effect accelerates
of amorphous silica which can be classified into silica fume, micro silica cement hydration and is more precisely termed as the seeding effect
and nano silica, etc., according to their particle size and physical [9,10,11]. Incorporation of supplementary cementitious materials
property. The distinct characteristics of UHPC such as workability and (SCMs) such as amorphous silica in cement may act as nucleation sites
mechanical strength are considerably dependent on physical properties for the growth of C-S-H [17], and similar effect can be anticipated by
and types of amorphous silica used. incorporating other mineral powders (e.g., quartz [13], rutile [14],
Amorphous silica, which consists solely or mostly of SiO2, plays a limestone [15,16], synthetic C–S–H [10,17]). In general, filler effect of
role in improving the rheology and the mechanical performance of amorphous silica is accepted to accelerate the hydration of the clinker
UHPC due to their inherited properties (e.g. high purity, spherical phases (especially, C3A and C3S) at an early age, while pozzolanic re-
particle with very fine size, high pozzolanic activity [2,49,51] and high action of amorphous silica starts at a later stage and is enhanced with
specific surface areas) [3]. One of commonly used amorphous silica is pH and temperature [2].
silica fume which is a by-product of industrial silicon production and it It should be noted that pozzolanic reaction of amorphous silica with
has particle sizes in the sub-micrometer range. The generally known CH to form C-S-H gel is limited due to the very low w/c ratio (< 0.25
behavior of amorphous silica in UHPC is twofold as follows. First is by mass) of UHPC system, instead the role of amorphous silica
⁎
Corresponding author.
E-mail address: ryu0505@kict.re.kr (G.S. Ryu).
https://doi.org/10.1016/j.cemconres.2017.11.002
Received 1 June 2017; Received in revised form 20 October 2017; Accepted 6 November 2017
Available online 12 November 2017
0008-8846/ © 2017 Elsevier Ltd. All rights reserved.
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
predominantly facilitates the filler effect [18]. Even though filler effect Table 1
and pozzolanic reaction were found to be clearly inclusive of each other Chemical composition of binder materials used in this study.
[5], the filler effect is a more notable phenomenon in UHPC than in
(wt%) OPC Micro silica-I Micro silica-II
other concrete blended with SCMs. The incorporation of a large amount
of amorphous silica in UHPC mixture and its low w/c ratio can promote XRD
filler effect rather than pozzolanic reaction. Especially during early ages Rietveld analysis
(< 24 h), amorphous silica is anticipated to most dominantly behave as
SiO2 21.23 C3S 59.2 92.0 93.8
a filler in UHPC, which increases hydration rates by seeding effect Al2O3 5.64 C2S 21.9 0.53 0.38
[19,20], while pozzolanic reaction is probably negligible due to the Fe2O3 3.38 C4AF 9.2 0.97 0.25
relatively low alkalinity of the pore solution at this stage [2]. CaO 61.4 C3A 3.6 0.48 0.03
Some researchers experimentally demonstrated an enhanced hy- MgO 2.20 Gypsum 2.3 1.18 –
TiO2 0.23 Anhydrite 1.9 – –
dration degree of cement at early age by incorporating silica fume with
K2O 1.15 Others 1.8 0.70 0.02
small size particles and high surface area, which effectively increases SO3 2.25 0.23 0.07
the extent of C-S-H nucleation [11,21,22]. However, the surface area of Na2O 0.11 0.56 0.06
amorphous silica is not always correlated with the extent of the seeding Cl 0.06 0.14 –
ZnO 0.15 0.17 –
effect, and its reactivity is also a governing factor. For instance, if one is
ZrO2 – – 4.16
easily dissolved due to its high reactivity, its filler effect is less likely
and the pozzolanic reaction is to be dominant. On the other hand, an-
other one with relatively low reactivity but greater particle size can be 2. Experimental procedure
more favorable for the filler effect, since undissolved particles can play
a role of nucleation seeding. In a previous study, it was found that the 2.1. Materials
reactivity of three types of silica (Pyrogenic silica, silica fume and
Stoeber silica) had a close relation with the specific surface area, sur- Ordinary Portland cement (OPC, ASTM C150 Type I) used in this
face silanol group density, total content of silanol groups and solubility study was provided by Asia Cement Corp., South Korea. Two types of
in alkaline suspension [4]. It was revealed that the degree of pozzolanic amorphous silica (micro silica-I and -II) were supplied by Elkem Corp.,
reaction was higher for Stoeber particles (with higher amount of silanol South Korea and S. Corp., China, respectively. Silica powder with dia-
group) than for the less reactive pyrogenic silica and silica fume (with meters of 1–5 μm was used as a fine filler, and micro sand with dia-
lower surface silanol group density and lower total amount of silanol meters of 100–800 μm were used as a fine aggregate.
groups). In their later study, silica fume and pyrogenic silica was found The chemical compositions of these materials are listed in Table 1.
to accelerate the alite hydration by increasing the surface for nucleation Micro silica-I and -II showed very similar chemical compositions in
of C-S-H phases whereas Stoeber particles showed no accelerating effect terms of SiO2, Al2O3, Fe2O3 and CaO, while the micro silica-I contained
[5]. 1.18% of MgO and the micro silica-II had no MgO. It is noted that only
Filler effect is more likely to accelerate the hydration of aluminate the micro silica-II contained 4.16% of ZrO2. The specific gravity of
phases, which normally gives rise to a second or shoulder peak in a micro silica-I and -II were 2.20 and 2.50, respectively. The miner-
calorimetric curve after the main peak associated with the hydration of alogical composition of the anhydrous OPC determined by XRD Riet-
alite, rather than that of calcium silicate phases [2,23]. The additions of veld analysis is also listed in Table 1.
the fine materials, i.e., corundum and rutile, have much more sig- The maximum water adsorption/desorption contents of micro silica-
nificant impact on the aluminate reaction than on the silicate reaction, I were 56.8 (P/P0 = 0.9730) and 6.78 cm3/g (P/P0 = 0.0965), re-
as the hydration of the aluminate phases is often more sensitive to spectively, and those of micro silica-II were 10.8 (P/P0 = 0.9466) and
nucleation effects [23]. In other studies [11,24], it was found that the 2.03 cm3/g (P/P0 = 0.0857), as measured using a BELSORP-aqua3
high surface area of amorphous silica has a high capacity to adsorb (BEL JAPAN, INC.) instrument. This property may affect the level of
sulfate ions, and the decreased sulfate concentration accelerates the slump flow of UHPC by adsorbing some of the mix water in the fresh
formation of monosulfate. At the same time, the change in the sulfate state. The amount of superplasticizer required to obtain high slump
concentration also influenced the dissolution and formation of sulfate flow of UHPC (> 750 mm) can be varied depend on the type of micro
containing phases [11]. silica with different adsorption content. For instance, micro silica with a
To date, the filler effect and pozzolanic reaction of amorphous silica higher water adsorption content requires a higher superplasticizer
in UHPC have been investigated in a limited number of studies. In more amount to reach similar flow.
detail, the influence of the two different behaviors (filler effect and The surface area was measured by nitrogen adsorption using a
pozzolanic reaction) of micro silica on the hydration and microstructure Micromeritics ASAP2420 by degasifying at 300 °C and 1.333 Pa
of UHPC has been poorly understood. In this regard, this paper in- (10 μmHg) for 2 h. The surface areas of micro silica-I and -II were 23.5
vestigated the role of micro silica in hydration and strength of UHPC. and 9.42 m2/g, respectively. The micro silica-II used in this study
Two types of micro silica with different extent of pozzolanic reactivity showed the lower surface area than the minimum specific area (15 m2/
and filler effect were considered: one is silica fume and another one is g) for silica fume stated in ASTM C1240.
amorphous silica containing a minor quantity of zirconium. The water The particle size distribution of the raw materials was measured
adsorption/desorption rate, surface area, and particle size of the micro using a laser particle-size analyzer (CILAS 1090L, CILAS, FRANCE), and
silica were measured, and the correlation of the results with the hy- is shown in Fig. 1. The mean particle size of the micro silica-I (0.31 μm)
dration and strength development of UHPC was discussed. The role of was lower than that of the micro silica-II (0.93 μm).
micro silica in UHPC were investigated with regard to their filler effect
and pozzolanic reaction by using analytical techniques; X-ray diffrac-
tion (XRD), thermogravimetry (TG), nuclear magnetic resonance 2.2. Mixture proportions and samples preparation
(NMR) spectroscopy, and mercury intrusion porosimetry (MIP).
The mixture proportions of UHPC are provided in Table 2. A water-
to-binder (cement + micro silica) ratio was 0.187 and a shrinkage re-
ducing agent/cement ratio was 0.01. Superplasticizer-to-cement ratios
for UHPC incorporating micro silica-I and -II were 0.023 and 0.062,
respectively. The UHPC incorporating the micro silica-II required much
69
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
70
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
Fig. 2. XRD patterns of raw materials and UHPC (△: C3S, □: C2S, ○: CH, ☆: Ettingite, +: C2F, X: C3A, ◇: Quartz, G: Gypsum, C-S-H, Z: ZrO2).
71
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
Fig. 3. DTG and TG results of (a) M1U-1 and M2U-1; (b) M1U-4 and
M2U-4; (c) M1U-28 and M2U-28.
3.2. Thermogravimetry (TG) temperature of around 100 °C due to the evaporation of free and phy-
sically bound water, the dehydration of C-S-H and ettringite. The
Fig. 3(a) shows the derivative thermogravimetry (DTG) and TG weight loss at this region can also result from the presence of third
curves for M1U-1 and M2U-1 cured at 20 °C and RH > 99% for 24 h. aluminate hydrate (TAH) species which decomposes at 70–90 °C [25]
The DTG curves of both samples showed a weight loss at the and will be discussed in Sec. 3.4 in detail. The weight loss at
72
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
29
Fig. 4. Si MAS NMR spectra of UHPC.
temperatures of around 150 °C was attributed to the dehydration of carbonation or pozzolanic reaction during the high temperature curing.
AFm [26]. The peak centered at 420 °C was associated with the dehy- However, the weight loss at the region between 620 and 710 °C asso-
droxylation of CH, and the peak between 620 and 710 °C was observed ciated with the decarbonation of CaCO3 was not increased in M1U-4
due to the decarbonation of CaCO3. The presence of C-S-H, ettringite compared to M1U-1, indicating that the carbonation of CH can be
and CH was observed in both M1U-1 and M2U-1, which is consistent considered negligible in M1U-4. Thus, it is likely that most of the CH in
with the XRD results for M1U-1 and M2U-1. M1U-4 was consumed by the pozzolanic reaction with micro silica-I to
The DTG and TG curves of M1U-4 and M2U-4 are shown in produce C-S-H during the curing at a temperature of 90 °C. The peak
Fig. 3(b). The sharp peak at 100 °C corresponding to the decomposition centered at 420 °C was observed in M2U-4 although the peak became
of ettringite was reduced, due to the thermal decomposition which took more diffuse than that in M2U-1, as seen in Fig. 3(b). The low pozzo-
place during the high temperature curing, while the peak at around lanic activity of the micro silica-II in the M2U samples might be due to
150 °C associated with the interlayer water removal of AFm was ob- the poor dispersion and agglomeration of micro silica-II [28], however,
served [26,27]. It should be noted that the weight loss at 420 °C cor- a measured slump flow (750 mm) of UHPC containing the micro silica-
responding to the dehydroxylation of CH was not identified in M1U-4. II was as high as that of UHPC containing the micro silica-I despite the
The absence of CH in M1U-4 may be attributed to the occurrence of fact that relatively lower amount of superplasticizer was used for M2U
73
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
Table 3
29
Deconvolution results for the Si MAS NMR spectra (%)a.
Sample C3S, C2S Q1 Q2(1Al) Q2b Q2p Q3(1Al) Q3 − 99 ppmb Q4 Al/Si ratioc MCLc,d
− 71 ppm −79 ppm − 81 ppm −83 ppm − 85 ppm − 90 ppm − 94 ppm − 110 ppm
M1U-1 36.7 9.6 6.7 2.0 8.6 1.9 0 0 34.5 0.12 10.1
M2U-1 36.2 9.3 0.4 3.1 6.3 0 0 0 44.8 0.01 6.2
M1U-4 31.2 11.2 12.3 3.5 21.9 5.1 2.4 1.5 13.1 0.09 16.0
M2U-4 29.6 9.7 5.5 2.2 13.0 2.8 1.5 1.1 34.7 0.08 11.6
M1U-28 28.6 10.2 11.5 3.4 22.1 5.6 2.2 1.4 14.9 0.10 17.9
M2U-28 29.7 15.3 5.1 2.1 9.9 2.6 0.7 1.5 33.1 0.07 7.5
3
2 ⎡Q1 + Q2 + Q2 (1Al) ⎤
MCLnc = ⎣ 2 ⎦
Q1 (1)
1 2
Q (1Al)
2
Al/Sinc =
Q1 + Q2 + Q2 (1Al) (2)
4[Q1 + Q2 + Q2 (1Al) + Q3 + 2Q3 (1Al)]
MCLc =
Q1 (3)
Q3 (1Al)
Al/Sic = 1
Q + Q2 + Q2 (1Al) + Q3 + Q3 (1Al) (4)
Q2 p − 2(Q3 + Q3 (1Al)) ≥0 (5)
The following was assumed to obtain the overall trend of the samples, which provided basis for the calculation of MCL.
The hydration product of UHPC in this study is believed to be poorly ordered crystalline C-(A)-S-H, meaning that the use of C-A-S-H model for the calculation of MCL may not be adequate
to predict the absolute value. However, this assumption does not affect the overall trends observed in the calculated MCL values as long as the method applied is consistent.
a
Example of spectral decomposition for the UHPC sample is shown in Fig. 4(e).
b
The resonance at 99 ppm is attributed to silicon at Q3 or Q4 site in silica fume. The curing at the temperature of 90 °C led to the depolymerization of Q4 network of the silica fume by
hydrolysis [33], which is supported by the fact that M1U-1 and M2U-1 before curing at the high temperature showed no resonance at 99 ppm.
c
The MCL and Al/Si ratio for noncross-linked C-(A-)S-H (NC) and cross-linked C-(A-)S-H structures (C) containing Q3 and/or Q3(1Al) sites were calculated by Eqs. (1)–(2) [45] and Eqs.
(3)–(4) [46], respectively.
d
In general, the structural constraints related to Q2 and Q3 for the cross-linked C-(A-)S-H products are specified as Eq. (5) [46].
mixtures. Thus, it is reasonable to attribute the low pozzolanic reaction reaction was. In summary, filler effect and pozzolanic effect of micro
of M2U samples to the low pozzolanic activity of micro silica-II, rather silica are influenced both by its physical properties (i.e., particle size
than its poor dispersion. Meanwhile, the presence of CH in M2U-4 is in and surface area) and the silanol group density, which can accordingly
close agreement with the XRD results for M2U-4, indicating that the affect the hydration of UHPC.
pozzolanic effect induced by the addition of micro silica-II was not Note that the weight loss at a temperature of 300 °C was observed in
dominant in M2U samples. M2U-28, while not in M1U-28. This peak is assigned to dehydroxylation
Fig. 3(c) shows the DTG and TG curves for M1U-28 and M2U-28. of AFm phase [26,27,29]. The lower pozzolanic activity of micro silica-
The peak associated with the decomposition of CH was still observed in II than that of micro silica-I may affect the presence of AFm. This me-
M2U-28. Despite the fact that all samples were cured in a water bath at chanism will be elucidated in detail with aid of 29Si and 27Al NMR
20 °C from the end of the high temperature curing to 28 days, the CH in results.
the M2U samples was not completely consumed by the pozzolanic re-
action with the micro silica-II, featuring a clear difference in the poz- 29
3.3. Si MAS NMR spectroscopy
zolanic activity between micro silica-I and -II in the UHPC.
These two different behaviors of micro silica are possibly attributed Fig. 4(a) shows the 29Si NMR spectra of the raw materials (OPC,
to its physical properties. Micro silica-II has a higher mean particle size micro silica-I and -II). The spectra of OPC showed narrow resonance at
than micro silica-I, and has a lower surface area. This property of micro − 71.7 ppm associated with Q0 site of belite (C2S) and broad resonance
silica-II may result in the lower level of pozzolanic reaction due to its between 66 and 78 ppm originating from alite (C3S) [30]. The spectra
inherent lower reactivity than micro silica-I. It makes sense that, all of micro silica-I and -II showed a broad signal centered at around
other things being equal, reactivity of micro silica increases as it is − 110 ppm which is assigned to amorphous SiO2.
finer. Meanwhile, micro silica-II contains 4.16% ZrO2 and micro silica-I 29
Si MAS NMR spectra of hydrated OPC are mostly dominated by
contains 1.18% MgO. The amount of ZrO2 and MgO in the two micro intense bands at −79.4 ppm, −83.5 ppm and − 85.3 ppm, which are
silica are very few, and no hydration product related to these compo- characteristic of silicate species in chain-end (Q1), bridging (Q2b) and
nents was identified through the XRD and 27Al NMR analysis. Thus, the paired (Q2p) sites of C-S-H, respectively [32,48]. In addition, the re-
chemical composition difference between the two micro silica cannot sonance at − 81 ppm corresponds to mid-groups, Q2(1Al) site, in which
be a main reason for the different behaviors. Another reason could be Al species substitutes for Si in the bridging site of C-S-H.
found in the literature [4]. The study showed that the reactivity of The 29Si NMR spectra of M1U-1 and M2U-1 in Fig. 4(b) showed
micro silica was highly associated with surface silanol group density, resonance at − 72 and − 110 ppm, which correspond to the anhydrous
total content of silanol groups and solubility in alkaline suspension. The OPC and the unreacted micro silica, respectively. The resonance at
higher amount of silanol group was, the higher degree of pozzolanic − 79 and −85 ppm in the spectra was observed in both samples, which
74
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
75
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
29
Fig. 5. Al MAS NMR spectra of UHPC.
different role played by the micro silica-I and -II in UHPC. That is, the In Fig. 5(d), the spectra of M1U-28 and M2U-28 are compared to
micro silica-I in M1U-4 predominantly facilitated pozzolanic effect by those of M1U-4 and M2U-4, respectively. From 4 d (i.e. after high
which most of the CH was consumed, as evidenced by the XRD, TG and temperature curing) to 28 d, the M1U and M2U samples were cured in a
29
Si NMR results, while the filler effect was predominant in the micro water bath at an ambient temperature of 20 °C. During this period, the
silica-II. The high pozzolanic activity of micro silica-I led to a relatively microstructure of hydration products in the UHPC was not changed
low Ca/Si ratio of C-S-H, and thus the level of Al substitution for Si in C- significantly.
S-H increased, in particular, upon the decomposition of ettringite. The In summary of the Si and Al NMR results, the incorporation of micro
relationship between a level of Al substitution for Si and a Ca/Si ratio of silica-I in M1U samples led to an increase in the MCL of SiO4 tetrahedra
C-S-H was also found in the 27Al NMR results from previous studies in C-S-H and promoting the level of Al substitution for Si in the bridging
[25,41,44]. In addition, the level of Al(IV) substitution in C-S-H af- tetrahedral chains of C-S-H, compared to the M2U samples in-
fected the Al(VI) in TAH; the intensity of signal corresponding to Al(VI) corporating the micro silica-II. Effectively, the Al uptake in the C-S-H is
in TAH was lower in M1U-4 accompanying with the higher level of Al favored when higher pozzolanic reaction is achieved, as confirmed by
(IV) substitution in C-S-H, but the opposite was in M2U-4. the Si & Al NMR results. In contrast, Al is mostly taken up by AFm and
These results confirm that the Al binding sites, Al(IV) and Al(VI), in TAH at the lower pozzolanic reaction where the chain length of C-S-H is
the hydration products of UHPC are strongly dependent on the type of relatively shorter, accordingly a lower fraction of Q2(1Al) and Q3(1Al)
micro silica used. The different behavior between micro silica-I (pre- sites in C-S-H is observed.
dominant with pozzolanic effect) and -II (predominant with filler ef-
fect), thus affected a Ca/Si ratio of C-S-H in UHPC. In case of micro
3.5. MIP results
silica-I, a Ca/Si ratio of C-S-H was decreased by the high pozzolanic
effect of micro silica-I, thus allowing preferential substitution of Al(IV)
The structure of pores with diameters of < 1 um in the samples as
for Si in C-S-H. Meanwhile, a Ca/Si ratio of C-S-H in the M2U samples
measured by MIP are strongly related to the dissolution of micro silica
was higher by the filler effect of micro silica-II, and the octahedrally
and the formation of hydration products. Due to the micro silica-I and
coordinated Al contributed to the formation of AFm and TAH [41,42].
-II possessing different pozzolanic effect (or filler effect), the dissolution
This is consistent with the 29Si NMR results. As shown in Figs. 4(c) and
degree of the micro silica and the type and amount of hydration pro-
(d), the fraction of Q2, Q2(1Al) and Q3(1Al) sites was higher in M1U
ducts varied accordingly; the 29Si and 27Al NMR results showed that
samples containing the micro silica-I than in M2U samples containing
higher pozzolanic activity of micro silica led to the higher dissolution
the micro silica-II. Similarly, it was also reported in a previous study
degree of micro silica and a reduction in the amount of octahedrally
that Al mostly tends to be octahedral-coordinated (i.e., AFm, AFt, and
coordinated aluminum (Al(VI)) site in AFm phases. Thus, the property
TAH [25,41,44]) when the Ca/Si ratio of C-S-H is higher than around
of micro silica used can affect the overall pore size distribution of
1.1, while it is likely to end up with tetrahedral coordination in C-A-S-H
UHPC.
at a lower Ca/Si ratio [42].
Fig. 6(a) shows that the volume of pores with diameters of < 7 nm
76
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
(Fig. 7). On one hand, one may assume that pozzolanic reaction of
micro silica with CH would result in a denser cement matrix, and hence
reduced porosity. However, M2U-4 incorporating micro silica-II with
relatively lower pozzolanic activity showed the pore size distribution
analogous to M1U-4 which showed higher pozzolanic reaction. This can
attributed to the filler effect of micro silica-II, minimizing the voids
between particles in the UHPC.
Fig. 6(c) shows that the volume of pores with diameters between 4
and 20 nm was remarkably reduced in M2U-28 compared to M2U-4,
while this was not reduced in M1U-28. This suggests that the additional
hydration of UHPC occurred from 4 to 28 d to more extent in M2U-28.
This is likely to be due to the pore-filling effect of additionally formed
C-S-H with Q1 silicate units, as revealed in the 29Si NMR results
(Fig. 4(d)) where the intensity of Q1 site was increased from 4 to 28 d.
In addition, this hydration products seemed to contribute to an increase
in the compressive strength of M2U-28.
77
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
Table 6
Hydration kinetics of UHPC according to three stages.
Predominant Predominant
Pozzolanic effect Filler effect
a
Seeding or pozzolanic effect was not evident at early ages (i.e. Stage I) in the present study. However, initiation of these effects at early ages is highly dependent on the properties of
amorphous silica used (i.e., reactivity, surface area, particle size) and the amount of superplasticizer used.
78
N.K. Lee et al. Cement and Concrete Research 104 (2018) 68–79
reactivity led to the increase in Al-substitution for Si in C-S-H and [23] G. Le Saout, K. Scrivener, Early hydration of Portland cement with corundum ad-
the denser structure, thus increasing the compressive strength. On dition, 16, Internationale Baustofftagung (ibausil). Weimar, Germany, 2006, pp.
409–416.
the other hand, the UHPC incorporating micro silica with relatively [24] H.J. Kuzel, Formation of AFm and Aft phases in hydrating Portland cements,
lower pozzolanic activity showed that the Al environment mostly Proceedings of the 16th International Conference on Cement Microscopy,
consists of AFm and TAH. At Stage III, further hydration of C3S and Duncanville, Texas, 1994, pp. 125–136.
[25] X. Pardal, F. Brunet, T. Charpentier, I. Pochard, A. Nonat, 27Al and 29Si solid-state
C2S occurred in the UHPC incorporating micro silica with relatively NMR characterization of calcium-aluminosilicate-hydrate, Inorg. Chem. 51 (3)
lower pozzolanic activity, increasing the amount of Q1 site in C-S-H (2012) 1827–1836.
and decreasing the porosity in the pore diameter region below [26] B.Z. Dilnesa, B. Lothenbach, G. Renaudin, A. Wichser, E. Wieland, Stability of
monosulfate in the presence of iron, J. Am. Ceram. Soc. 95 (10) (2012) 3305–3316.
10 nm. Consequently, a significant increase in the compressive [27] S.M. Leisinger, B. Lothenbach, G. Le Saout, C.A. Johnson, Thermodynamic mod-
strength was achieved. eling of solid solutions between monosulfate and monochromate 3CaO∙ Al2O3 ∙ Ca
[(CrO 4)x(SO4)1-x]∙nH2O, Cem. Concr. Res. 42 (1) (2012) 158–165.
[28] M.C. Juenger, R. Siddique, Recent advances in understanding the role of supple-
Acknowledgments
mentary cementitious materials in concrete, Cem. Concr. Res. 78 (2015) 71–80.
[29] S. Medvešček, R. Gabrovšek, V. Kaučič, A. Meden, Hydration products in water
This research was supported by a grant (13SCIPA02) from Smart suspension of Portland cement containing carbonates of various solubility, Acta
Civil Infrastructure Research Program funded by Ministry of Land, Chim. Slov. 53 (2) (2006).
[30] J. Skibsted, H.J. Jakobsen, C. Hall, Quantification of calcium silicate phases in
Infrastructure and Transport (MOLIT) of Korea government and Korea Portland cements by 29Si MAS NMR spectroscopy, J. Chem. Soc. Faraday Trans. 91
Agency for Infrastructure Technology Advancement (KAIA). (1995) 4423–4430.
[32] R.J. Myers, E. L'Hôpital, J.L. Provis, B. Lothenbach, Effect of temperature and
aluminium on calcium (alumino) silicate hydrate chemistry under equilibrium
References conditions, Cem. Concr. Res. 68 (2015) 83–93.
[33] T.T.H. Bach, C.C.D. Coumes, I. Pochard, C. Mercier, B. Revel, A. Nonat, Influence of
[1] A.E. Naaman, K. Wille, The path to ultra-high performance fiber reinforced concrete temperature on the hydration products of low pH cements, Cem. Concr. Res. 42 (6)
(UHP-FRC): five decades of progress, in: M. Schmidt, E. Fehling, C. Glotzbach, et al. (2012) 805–817.
(Eds.), Proceedings of 3rd Hipermat: International Symposium on UHPC and [34] C.A. Love, I.G. Richardson, A.R. Brough, Composition and structure of C–S–H in
Nanotechnology for High Performance Construction Materials, Kassel University white Portland cement–20% metakaolin pastes hydrated at 25 °C, Cem. Concr. Res.
Press, Kassel, 2012, pp. 3–16. 37 (2) (2007) 109–117.
[2] B. Lothenbach, K. Scrivener, R.D. Hooton, Supplementary cementitious materials, [35] A.V. Girao, I.G. Richardson, R. Taylor, R.M.D. Brydson, Composition, morphology
Cem. Concr. Res. 41 (12) (2011) 1244–1256. and nanostructure of C–S–H in 70% white Portland cement—30% fly ash blends
[3] T. Oey, A. Kumar, J.W. Bullard, N. Neithalath, G. Sant, The filler effect: the influ- hydrated at 55 °C, Cem. Concr. Res. 40 (2010) 1350–1359.
ence of filler content and surface area on cementitious reaction rates, J. Am. Ceram. [36] E. L'Hôpital, B. Lothenbach, D.A. Kulik, K. Scrivener, Influence of calcium to silica
Soc. 96 (6) (2013) 1978–1990. ratio on aluminium uptake in calcium silicate hydrate, Cem. Concr. Res. 85 (2016)
[4] T. Oertel, F. Hutter, U. Helbig, G. Sextl, Amorphous silica in ultra-high performance 111–121.
concrete: first hour of hydration, Cem. Concr. Res. 58 (2014) 131–142. [37] J.J. Chen, J.J. Thomas, H.F.W. Taylor, H.M. Jennings, Solubility and structure of
[5] T. Oertel, U. Helbig, F. Hutter, H. Kletti, G. Sextl, Influence of amorphous silica on calcium silicate hydrate, Cem. Concr. Res. 34 (2004) 1499–1519.
the hydration in ultra-high performance concrete, Cem. Concr. Res. 58 (2014) [38] G.K. Sun, J.F. Young, R.J. Kirkpatrick, The role of Al in C–S–H: NMR, XRD, and
121–130. compositional results for precipitated samples, Cem. Concr. Res. 36 (2006) 18–29.
[6] H.W. Krauss, H. Budelmann, Hydration kinetics of cement paste with very fine inert [39] I. Schachinger, H. Hilbig, T. Stengel, E. Fehling, Effect of curing temperature at an
mineral additives, Proceedings RILEM 79, Hongkong, 2011, pp. 58–65. early age on the long-term strength development of UHPC, 2nd International
[7] A. Kumar, S. Bishnoi, K.L. Scrivener, Modelling early age hydration kinetics of alite, Symposium on Ultra High Performance Concrete, 10 2008, March, pp. 205–213.
Cem. Concr. Res. 42 (2012) 903–918. [40] J.E. Rossen, B. Lothenbach, K.L. Scrivener, Composition of C–S–H in pastes with
[8] H.W. Krauss, H. Budelmann, Agglomeration und räumliche Anordnung von increasing levels of silica fume addition, Cem. Concr. Res. 75 (2015) 14–22.
Feinstoffpartikeln in Zementleim - physikalische Mechanismen und Einfluss auf die [41] M.D. Andersen, H.J. Jakobsen, J. Skibsted, A new aluminum hydrate species in
Hydratation, in: F. Winnefeld, F. Deschner (Eds.), Proceedings of Tagung hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy,
Bauchemie, GDCH- Fachgruppe Bauchemie, Dübendorf, 2012, pp. 35–42. Cem. Concr. Res. 36 (2006) 3–17.
[9] F. Deschner, F. Winnefeld, B. Lothenbach, et al., Hydration of Portland cement with [42] B. Lothenbach, A. Nonat, Calcium silicate hydrates: solid and liquid phase com-
high replacement by siliceous fly ash, Cem. Concr. Res. 42 (2012) 1389–1400. position, Cem. Concr. Res. 78 (2015) 57–70.
[10] J.J. Thomas, H.M. Jennings, J.J. Chen, Influence of nucleation seeding on the hy- [43] E. Zhao, S.E. Hardcastle, G. Pacheco, A. Garcia, A.L. Blumenfeld, J.J. Fripiat,
dration mechanisms of tricalcium silicate and cement, J. Phys. Chem. C 113 (2009) Aluminum-doped mesoporous zirconia obtained from anionic surfactants,
4327–4334. Microporous Mesoporous Mater. 31 (1) (1999) 9–21.
[11] G. Land, D. Stephan, The influence of nano-silica on the hydration of ordinary [44] G. Renaudin, J. Russias, F. Leroux, C. Cau-dit-Coumes, F. Frizon, Structural char-
Portland cement, J. Mater. Sci. 47 (2) (2012) 1011–1017. acterization of C–S–H and C–A–S–H samples—part II: local environment in-
[13] V. Rahhal, R. Talero, Early hydration of Portland cement with crystalline mineral vestigated by spectroscopic analyses, J. Solid State Chem. 182 (2009) 3320–3329.
additions, Cem. Concr. Res. 35 (7) (2005) 1285–1291. [45] I.G. Richardson, G.W. Groves, The incorporation of minor and trace elements into
[14] W.A. Gutteridge, J.A. Dalziel, Filler cement: the effect of the secondary component calcium silicate hydrate (C-S-H) gel in hardened cement pastes, Cem. Concr. Res. 23
on the hydration of Portland cement: part 2: fine hydraulic binders, Cem. Concr. (1) (1993) 131–138.
Res. 20 (6) (1990) 853–861. [46] R.J. Myers, S.A. Bernal, R. San Nicolas, J.L. Provis, Generalized structural de-
[15] B. Lothenbach, G. Le Saout, E. Gallucci, K. Scrivener, Influence of limestone on the scription of calcium–sodium aluminosilicate hydrate gels: the cross-linked sub-
hydration of Portland cements, Cem. Concr. Res. 38 (6) (2008) 848–860. stituted tobermorite model, Langmuir 29 (2013) 5294–5306.
[16] M. Antoni, J. Rossen, F. Martirena, K. Scrivener, Cement substitution by a combi- [47] F. Brunet, T. Charpentier, C.N. Chao, H. Peycelon, A. Nonat, Characterization by
nation of metakaolin and limestone, Cem. Concr. Res. 42 (12) (2012) 1579–1589. solid-state NMR and selective dissolution techniques of anhydrous and hydrated
[17] W.A. Gutteridge, J.A. Dalziel, Filler cement: the effect of the secondary component CEM V cement pastes, Cem. Concr. Res. 40 (2) (2010) 208–219.
on the hydration of Portland cement: part I. A fine non-hydraulic filler, Cem. Concr. [48] J. Skibsted, M.D. Andersen, The effect of alkali ions on the incorporation of alu-
Res. 20 (5) (1990) 778–782. minum in the calcium silicate hydrate (C–S–H) phase resulting from Portland ce-
[18] T. Oertel, F. Hutter, R. Tänzer, U. Helbig, G. Sextl, Primary particle size and ag- ment hydration studied by 29Si MAS NMR, J. Am. Ceram. Soc. 96 (2) (2013)
glomerate size effects of amorphous silica in ultra-high performance concrete, Cem. 651–656.
Concr. Compos. 37 (2013) 61–67. [49] W. Huang, H. Kazemi-Kamyab, W. Sun, K. Scrivener, Effect of replacement of silica
[19] J. Hjorth, J. Skibsted, H.J. Jakobsen, 29Si MAs NMR studies of Portland cement fume with calcined clay on the hydration and microstructural development of eco-
components and effects of microsilica on the hydration reaction, Cem. Concr. Res. UHPFRC, Mater. Des. 121 (2017) 36–46.
18 (1988) 789–798. [50] A. Korpa, T. Kowald, R. Trettin, Phase development in normal and ultra high per-
[20] H. Justness, P. Colombet, et al. (Ed.), Kinetics of Reaction in Cementitious Pastes formance cementitious systems by quantitative X-ray analysis and thermoanalytical
Containing Silica Fume as Studied by 29Si MAS NMR, Nuclear Magnetic Resonance methods, Cem. Concr. Res. 39 (2) (2009) 69–76.
Spectroscopy of Cement-Based Materials, Springer, Berlin, 1998, pp. 245–267. [51] H. Zanni, M. Cheyrezy, V. Maret, S. Philippot, P. Nieto, Investigation of hydration
[21] J. Bjornstrom, A. Martinelli, A. Matic, L. Borjesson, I. Panas, Accelerating effects of and pozzolanic reaction in reactive powder concrete (RPC) using 29Si NMR, Cem.
colloidal nano silica for beneficial calcium-silicate-hydrate formation in cement, Concr. Res. 26 (1) (1996) 93–100.
Chem. Phys. Lett. 392 (2004) 242–248. [52] N.K. Lee, K.T. Koh, S.H. Park, G.S. Ryu, Microstructural investigation of calcium
[22] A.C.A. Muller, K.L. Scrivener, J. Skibsted, A.M. Gajewicz, P.J. McDonald, Influence aluminate cement-based ultra-igh performance concrete (UHPC) exposed to high
of silica fume on the microstructure of cement pastes: new insights from 1H NMR temperatures, Cem. Concr. Res. 102 (2017) 109–118.
relaxometry, Cem. Concr. Res. 74 (2015) 116–125.
79