# Microstructural Study of Hydration of C3S in the Presence of Calcium Nitrate Using Scanning Transmission X-Ray Microscopy (STXM)

Authors: Qinfei Li; Yang Wang; Guoqing Geng; Heng Chen; Pengkun Hou; Xin Cheng; Paulo J. M. Monteiro; Shifeng Huang; Jae Hong Kim
Journal: Journal of Nanomaterials
 (2020)

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## Abstract

Calcium nitrate (CN) is used widely as an effectively inorganic setting accelerator and antifreeze admixture in concrete structures. In this paper, the multiscale investigation of CN on the hydration of C3S was studied by scanning transmission X-ray microscopy (STXM) combined with near-edge X-ray absorption fine structure (NEXAFS), 29Si MAS NMR, calorimetry, scanning electron microscope, and N2 absorption. It was concluded that the calcium silicate hydrate (C-S-H) surrounds the unhydrated C3S at 1-day hydrated C3S in the presence of calcium nitrate, while portlandite is partly in transformation and is formed partly. Based on Ca L3,2-edge NEXAFS spectra for 1-day hydrated C3S particle, calcium nitrate does not change the structure of the asymmetrically 7-fold coordination of calcium in the C-S-H. Calcium nitrate can accelerate the hydration of C3S to some extent and polymerization of the silicate chains within C-S-H considerably at early age, resulting in the increasing specific surface area.


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## Body

## 1. Introduction

With the rapid speed of economic and industrial development, concrete has become the most widely used construction material. Today, many admixtures are used inside the concrete to protect it from freezing by accelerating cement hydration and depressing the freezing point of the aqueous solution [1]. The application of antifreeze admixtures is originally from Russia, and it is technologically convenient and beneficial for winter concreting.Calcium nitrate (Ca(NO3)2, CN) is an effective chloride-free setting accelerator and antifreeze admixture [1–4]. Ca(NO3)2 is well known to have the ability to improve the early compressive strength [5] and accelerate the hydration of cement [2–4]. Justnes and Nygaard studied the changes in the microstructure of cement paste and concrete in the presence of Ca(NO3)2 and concluded that Ca(NO3)2 can lower the amount of calcium hydroxide (CH) in hydrated cement pastes and change the morphology of CH to larger clusters, as well as increase the porosity of the OPC paste [6]. Some studies suggest that calcium nitrate may form a complex salt with aluminate phase in cement, and the accelerating efficiency of Ca(NO3)2 depended on the cement type, especially on belite content [4, 7]. However, it was proved by X-ray diffraction that the presence of Ca(NO3)2 does not affect the stability of ettringite and forms hardly the compound C3A·Ca(NO3)2·10H2O7. Harald and Erik proposed the mechanism for accelerating the setting of Ca(NO3)2: (1) an increased concentration of Ca2+ leads to a faster supersaturation of the fluid for forming CH, while (2) Ca(NO3)2 decreases the concentration of SO42- leading to slower formation of ettringite which will shorten the onset of C3A hydration [8]. However, there are few literatures on Ca(NO3)2 obtained from the hydration of C3S regarding its chemical and physical properties. Therefore, it is essential to investigate the effect of Ca(NO3)2 of the hydrated C3S at it microstructure level.Scanning transmission X-ray microscopy (STXM) is a promising technique in further understanding the structure and the properties of amorphous and crystalline materials, such as C-S-H phase [9–14]. Combined with near-edge X-ray absorption fine structure (NEXAFS), STXM provides the information on both morphology and X-ray Absorption Spectroscopy (XAS) at submicron-scale level. The object is to explore the mechanism of calcium nitrate during the hydration of C3S as an accelerator at the molecular level. It will improve understanding of the accelerating role of calcium nitrate on the chemical information of C-S-H, bringing a state-of-the art step closer to the development of admixtures for Portland cement and advanced concrete structures.


## 2. Materials and Experimental Methods

### 2.1. Materials

Triclinic C3S powders were purchased from CTL Group (Skokie, IL), which were passed through sieve #325 (45 μm). The analytical reagent of Ca(NO3)2·4H2O was used by 2 wt% of C3S powders, which was purchased from Sigma-Aldrich. The boiled deionized water after cooling was used in the preparation of the C3S pastes with different liquid-to-solid ratios. To avoid the carbonation of carbon dioxide into the samples, the C3S pastes were maintained in the CryoTube™ vials (1.8 mL) under the protection of N2 gas at room temperature and then sealed in a vacuum bag. In this paper, we followed the methods of STXM and 29Si MAS NMR [15].


### 2.2. Experimental Methods

#### 2.2.1. Isothermal Calorimetry

The samples were prepared, respectively, by 0.4 and 0.5 liquid/solid ratio. About 2 g of the fresh paste was placed into a glass Admix ampule with 20 mL, and the ampule was sealed before transferring into the chamber in the isothermal calorimetry. The data were collected continuously by isothermal calorimetry (TA Instruments, Model TAM Air) during the 36-hour hydration of the samples.


#### 2.2.2. X-Ray Diffraction

The samples of the triclinic C3S and hydrated C3S with the addition of Ca(NO3)2 at 1, 3, 7, and 28 days were tested using a PANalytical X’Pert Pro diffractometer equipped with a Co X-ray tube (λ=1.79Å) and the rapid X’celerator detector. XRD was used to identify crystalline phases from a 2𝜃 value of 5–80° with a step of 0.02°.


#### 2.2.3.29Si MAS NMR and N2 Absorption

The samples of C3S pastes with calcium nitrate were prepared by 0.5 of the liquid-to-solid ratio for 1, 3, 7, and 28 days of hydration. The hydration of the samples was stopped by isopropanol, and then, samples were dried under the vacuum oven for 3 days. The samples were grounded into powders for solid-state NMR spectra (Bruker MSL-300 spectrometer). The parameters of NMR measurement followed the method of Li et al. [15]. Thereafter, the samples were crushed into fragments (≤4.75 mm) for N2 sorption measurement (Micromeritics ASAP 2000), which is performed at the School of Municipal and Environmental Engineering, Harbin Institute of Technology.


#### 2.2.4. Scanning Transmission X-Ray Microscopy and SEM

Scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) was performed at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) beamline 5.3.2.1 (350-2500 eV) [16]. Anhydrous triclinic C3S powder was mixed with 0.004 g/mL Ca(NO3)2 solution with a liquid-to-solid ratio of 5.0. C3S pastes were maintained in the CryoTube™ vials (1.8 mL) under the protection of N2 gas at 23°C and then sealed in a vacuum against carbonation. After 1 day of hydration, the C3S paste was ground and dispersed with deionized water for STXM measurement. Axis 2000 software (Version 2.1) was used to analyze the date of the NEXAFS spectra collected from STXM. The morphology of the paste was also observed by the scanning electron microscope (Quattro S from Thermo Fisher Scientific).


## 2.1. Materials

Triclinic C3S powders were purchased from CTL Group (Skokie, IL), which were passed through sieve #325 (45 μm). The analytical reagent of Ca(NO3)2·4H2O was used by 2 wt% of C3S powders, which was purchased from Sigma-Aldrich. The boiled deionized water after cooling was used in the preparation of the C3S pastes with different liquid-to-solid ratios. To avoid the carbonation of carbon dioxide into the samples, the C3S pastes were maintained in the CryoTube™ vials (1.8 mL) under the protection of N2 gas at room temperature and then sealed in a vacuum bag. In this paper, we followed the methods of STXM and 29Si MAS NMR [15].


## 2.2. Experimental Methods

### 2.2.1. Isothermal Calorimetry

The samples were prepared, respectively, by 0.4 and 0.5 liquid/solid ratio. About 2 g of the fresh paste was placed into a glass Admix ampule with 20 mL, and the ampule was sealed before transferring into the chamber in the isothermal calorimetry. The data were collected continuously by isothermal calorimetry (TA Instruments, Model TAM Air) during the 36-hour hydration of the samples.


### 2.2.2. X-Ray Diffraction

The samples of the triclinic C3S and hydrated C3S with the addition of Ca(NO3)2 at 1, 3, 7, and 28 days were tested using a PANalytical X’Pert Pro diffractometer equipped with a Co X-ray tube (λ=1.79Å) and the rapid X’celerator detector. XRD was used to identify crystalline phases from a 2𝜃 value of 5–80° with a step of 0.02°.


### 2.2.3.29Si MAS NMR and N2 Absorption

The samples of C3S pastes with calcium nitrate were prepared by 0.5 of the liquid-to-solid ratio for 1, 3, 7, and 28 days of hydration. The hydration of the samples was stopped by isopropanol, and then, samples were dried under the vacuum oven for 3 days. The samples were grounded into powders for solid-state NMR spectra (Bruker MSL-300 spectrometer). The parameters of NMR measurement followed the method of Li et al. [15]. Thereafter, the samples were crushed into fragments (≤4.75 mm) for N2 sorption measurement (Micromeritics ASAP 2000), which is performed at the School of Municipal and Environmental Engineering, Harbin Institute of Technology.


### 2.2.4. Scanning Transmission X-Ray Microscopy and SEM

Scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) was performed at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) beamline 5.3.2.1 (350-2500 eV) [16]. Anhydrous triclinic C3S powder was mixed with 0.004 g/mL Ca(NO3)2 solution with a liquid-to-solid ratio of 5.0. C3S pastes were maintained in the CryoTube™ vials (1.8 mL) under the protection of N2 gas at 23°C and then sealed in a vacuum against carbonation. After 1 day of hydration, the C3S paste was ground and dispersed with deionized water for STXM measurement. Axis 2000 software (Version 2.1) was used to analyze the date of the NEXAFS spectra collected from STXM. The morphology of the paste was also observed by the scanning electron microscope (Quattro S from Thermo Fisher Scientific).


## 2.2.1. Isothermal Calorimetry

The samples were prepared, respectively, by 0.4 and 0.5 liquid/solid ratio. About 2 g of the fresh paste was placed into a glass Admix ampule with 20 mL, and the ampule was sealed before transferring into the chamber in the isothermal calorimetry. The data were collected continuously by isothermal calorimetry (TA Instruments, Model TAM Air) during the 36-hour hydration of the samples.


## 2.2.2. X-Ray Diffraction

The samples of the triclinic C3S and hydrated C3S with the addition of Ca(NO3)2 at 1, 3, 7, and 28 days were tested using a PANalytical X’Pert Pro diffractometer equipped with a Co X-ray tube (λ=1.79Å) and the rapid X’celerator detector. XRD was used to identify crystalline phases from a 2𝜃 value of 5–80° with a step of 0.02°.


## 2.2.3.29Si MAS NMR and N2 Absorption

The samples of C3S pastes with calcium nitrate were prepared by 0.5 of the liquid-to-solid ratio for 1, 3, 7, and 28 days of hydration. The hydration of the samples was stopped by isopropanol, and then, samples were dried under the vacuum oven for 3 days. The samples were grounded into powders for solid-state NMR spectra (Bruker MSL-300 spectrometer). The parameters of NMR measurement followed the method of Li et al. [15]. Thereafter, the samples were crushed into fragments (≤4.75 mm) for N2 sorption measurement (Micromeritics ASAP 2000), which is performed at the School of Municipal and Environmental Engineering, Harbin Institute of Technology.


## 2.2.4. Scanning Transmission X-Ray Microscopy and SEM

Scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) was performed at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory (LBNL) beamline 5.3.2.1 (350-2500 eV) [16]. Anhydrous triclinic C3S powder was mixed with 0.004 g/mL Ca(NO3)2 solution with a liquid-to-solid ratio of 5.0. C3S pastes were maintained in the CryoTube™ vials (1.8 mL) under the protection of N2 gas at 23°C and then sealed in a vacuum against carbonation. After 1 day of hydration, the C3S paste was ground and dispersed with deionized water for STXM measurement. Axis 2000 software (Version 2.1) was used to analyze the date of the NEXAFS spectra collected from STXM. The morphology of the paste was also observed by the scanning electron microscope (Quattro S from Thermo Fisher Scientific).


## 3. Results and Discussion

### 3.1. Calorimetry

Figure1 shows the isothermal calorimetry data for C3S hydrated with calcium nitrate prepared under different liquid-to-solid ratio (L/S). Without the addition of calcium nitrate, the height of the early rate peak of C3S paste with L/S=0.5 increases, and the launch of the accelerating period is earlier. Commonly, the early hydration rate of C3S paste with L/S=0.5 develops more quickly than that of L/S=0.4; however, the presence of calcium nitrate is opposite due to more nucleation sites in C3S paste. The addition of calcium nitrate has a significant accelerating effect. When calcium nitrate is absent, the accelerating effect is greater under L/S=0.4 compared with L/S=0.5. But the addition of calcium nitrate makes the induction period slightly eliminate. Calcium nitrate can prompt the homogeneous nucleation [17] since the high abundance of Ca2+ in the pore solution combined with silicate ions dissolved from C3S. The early hydration of C3S paste is accelerated by calcium nitrate, which provides the development of pore structure and hydration products of C3S paste.Figure 1
Isothermal calorimetry of C3S pastes with different L/S and calcium nitrate.


### 3.2. N2 Sorption

According to the IUPAC classification, the hysteresis loops for all isotherms obtained from C3S samples are not of Type IV but of Type H3 due to no indication of a plateau at high P/P0 in Figure 2. Each adsorption branch has the similar feature of the typical Type II without limiting adsorption at high P/P0, and the desorption branch exhibits a different path before reaching a critical P/P0, which implies aggregates of plate-like particles resulting in slit-shaped pores. The C3S pastes for hydrating 3 and 7 days in Figure 2(a) have a narrower width of the hysteresis loop, while that of 28 days has the largest. However, the presence of calcium nitrate expands the hysteresis loop since hydrating for 3 days.Figure 2
Physisorption isotherms for C3S pastes with different hydration times in the (a) absence and (b) presence of calcium nitrate.
(a)
(b)The specific surface area results are shown in Table1. Since the Langmuir method is based on monolayer adsorption, the values for the Langmuir area are generally higher than those for the BET area. The specific surface area of C3S pastes is enhanced with an increase of hydration times whether the existence of calcium nitrate is included or excluded. However, the presence of calcium nitrate can increase the specific surface area of C3S paste. C3S can react quickly with water to form an amorphous phase, calcium silicate hydrates (C-S-H) with many gel pores, and calcium nitrate can accelerate the hydration of C3S resulting in the increasing specific surface area.Table 1
Specific surface area of C3S pastes with different hydration times (m2/g).
Sample
C3S 3 d
C3S 7 d
C3S 28 d
CN 3 d
CN 7 d
CN 28 d
BET area
9.16
11.29
33.52
15.89
25.95
38.52
Langmuir area
12.92
16.26
47.19
22.88
37.59
54.71For comparison purposes, the pore size distributions (PSD) are of very great significance as shown in Figure3. Pore size distributions are calculated by the Kelvin equation ranging from 2 to 50 nm. The mesopores in all samples are assessed by N2 sorption locating primarily at around 3.5 nm, while the gel pores cannot be addressed due to porewidths<2nm. However, the addition of calcium nitrate makes the pore width shift slightly up to about 4 nm with the increasing hydration time. These mesopores smaller than 50 nm play an important part in drying shrinkage and creep.Figure 3
BJH desorption PSD comparison for C3S pastes in the (a) absence and (b) presence of calcium nitrate.
(a)
(b)


### 3.3. STXM Analysis

As mentioned above, the development of the hydration products of C3S paste is also affected by calcium nitrate. Figure4 shows the XRD patterns of triclinic C3S and hydrated C3S pastes with calcium nitrate. In the presence of calcium nitrate, unhydrated C3S remains slightly at 7-day hydration since the reactivity of triclinic C3S is lower than monoclinic C3S. The feature peaks of portlandite are occurring at 1-day hydration of C3S pastes, while the morphology of portlandite presented the plate-like crystals surrounded by unhydrated C3S and C-S-H gel as shown in Figure 5.Figure 4
XRD patterns of triclinic C3S and C3S pastes with calcium nitrate.Figure 5
SEM images of 1-day hydration of C3S paste with calcium nitrate.Figure6 presents the single image of 1 d hydrated C3S taken at 340 eV (Figure 6(a)) and Ca L3,2-edge NEXAFS spectra (Figure 6(c)) of a selected area in Figure 6(a). Based on previous studies [18], the Ca L3,2-edge NEXAFS spectra of Ca(OH)2, anhydrous C3S, and pure C-S-H (in 17 d hydrated C3S) were investigated, respectively, in ways of STXM with NEXAFS in Figure 6(a). Each of these spectra is unique in terms of the peak shape, positions, and the energy splitting, which has been used as a fingerprint for identifications and investigations of Ca structure. Ca L3,2-edge NEXAFS spectra provide calcium coordination environment and characterize conveniently amorphous and crystalline Ca-containing materials.Figure 6
STXM results of 1 d hydrated C3S with calcium nitrate: (a) single image taken at 340 eV, (b) RGB overlay maps using SVD based on NEXAFS spectra of Ref. [18], (c) Ca L3,2-edge NEXAFS spectra of selected areas in (a).
(a)
(b)
(c)
(d)The observed multiple peak patterns of CaL3,2-edge NEXAFS spectra consist of two main spin-orbit-related peaks (a2 and b2) corresponding, respectively, to L3 and L2, along with several smaller peaks (a1 and b1) leading to the main peaks [19] (Figure 6(a)). The experimental resolution for the spectra is approximately less than 0.1 eV. The magnitudes and symmetry of the crystal field of calcium in the first coordination sphere result in crystal field splitting, which is the origin of this multipeak pattern [20]. The peak positions and energy separation values (ΔL3a2‐a1 and ΔL2b2‐b1) are associated with the symmetry of Ca-O sheet in C-S-H structure.CaL3,2-edge NEXAFS spectra of a selected area in Figure 6(c) show the different peak shapes, peak positions, and energy separations. Ca L3,2-edge NEXAFS for Areas 1, 2, 6, and 8 has the splitting energy with 1.3 and 1.2 eV for a2‐a1 and b2‐b1 and peak intensity ratios between a1/a2 and b1/b2 in agreement with the results of anhydrous C3S. Well-developed crystalline Ca(OH)2 with the largest splitting energy values and peak intensity ratios [18] are shown in Figure 6(a). Moreover, Bae et al. [18] investigated the 17 d hydrated C3S paste with water-to-solid ratio of 10 and concluded that the C-S-H of 17 d hydrated C3S has a very similar local structure around Ca but has less crystallinity comparing to synthetic C-S-H. Ca L3,2-edge NEXAFS spectra of C-S-H have energy separation 1.1 and 1 eV for a2‐a1 and b2‐b1 and the lowest peak intensity ratios [18], while the energy separation of 1.1 and 1.1 eV of Areas 3, 5, and 7 in one particle of 1 d hydrated C3S with calcium nitrate has the lowest peak intensity ratios. Therefore, calcium nitrate does not change the asymmetric 7-fold coordination of calcium in the calcium silicate hydrate (C-S-H), the primary hydration product.RGB overlay maps using Singular Value Decomposition (SVD) based on NEXAFS spectra obtained previously from Ref. [18] of Ca(OH)2, C-S-H, and anhydrous C3S are shown in Figure 6(a). Since various chemical components have unique features for NEXAFS spectra, the reference spectra obtained from known components were used to differentiate and visualize phases in a sample [21]. It was observed in the C3S particles under calcium nitrate solution that there are many magenta pixels (M = R + B = Ca(OH)2+unhydrated C3S) at the center in Figure 6(d) indicating that the unhydrated C3S in those pixels is transforming to crystalline Ca(OH)2. There are, however, a few cyan pixels (C = G + B = C-S-H+unhydrated C3S) at the boundary indicating that unhydrated C3S in that pixel is transforming to C-S-H, but there are few yellow pixels (Y = R + G = Ca(OH)2+C-S-H). Under the addition of calcium nitrate, the amorphous C-S-H surrounds the unhydrated C3S. However, portlandite is partly in transformation in Figure 6(d), while the formation of Ca(OH)2 partly occurs in Figure 5. Ca(NO3)2 can lower the amount of calcium hydroxide (CH) in hydrated cement pastes [6]. On the other hand, Ca2+ is the top diffusivity of cations, while NO3- is located at penultimate order, ranked in order of the effectiveness as accelerators [22–24]. Therefore, calcium nitrate can accelerate the hydration of C3S to some extent, but it is not the most effective one, such as CaCl2.


### 3.4.29Si MAS NMR Analysis

29Si MAS NMR plots for hydrated C3S with different hydration times in the absence or presence of Ca(NO3)2 are shown in Figure 7, and the results of the associated spectral deconvolutions are presented in Table 2. The connectivity of SiO4 tetrahedra, Qn, is used to describe various types of monomer, dimer, trimer, and tetramer, where n represents the number of bridging oxygens (Si-O-Si): Q0 site is isolated SiO4 tetrahedra, Q1 is SiO4 tetrahedra present in end units of a silicate chain, Q2 is a middle group, Q3 is a branching site, and Q4 sites link to four other SiO4 tetrahedra in a three-dimensional network. Amorphous C-S-H initially contains mainly dimeric silicate [25–27], while C3S includes nine inequivalent SiO4 tetrahedra (Q0 sites) between -69 ppm and -75 ppm [28].Figure 7
29Si MAS NMR spectra of C3S pastes as a function of hydration time in the (a) absence and in the (c) presence of calcium nitrate and deconvoluted spectrum for 28 d hydrate sample in the (b) absence and in the (d) presence of calcium nitrate.
(a)
(b)
(c)
(d)Table 2
29Si MAS NMR analysis for hydrated C3S paste at 25°C for hydration period of 1, 3, 7, and 28 days.
Samples
Percentage of integral intensities ofQn (%)
Q2/Q1
Q0-74 ppm
Q1-78 ppm
Q2-83 ppm
Q3-89 ppm
C3S_1 d
33.2
64.4
2.4
—
0.04
C3S_3 d
20.7
43.2
30.6
5.5
0.71
C3S_7 d
11.5
37.2
43.9
7.4
1.18
C3S_28 d
11.9
14.4
53.8
20.0
3.74
C3S+Ca(NO3)2_1 d
15.2
36.1
40.1
8.6
1.11
C3S+Ca(NO3)2_3 d
6.5
34.1
46.5
12.9
1.37
C3S+Ca(NO3)2_7 d
1.0
38.7
37.3
23.0
0.97
C3S+Ca(NO3)2_28 d
3.7
22.3
52.6
21.4
2.36In Figure7, 29Si MAS NMR spectra were fitted by the Gaussian functions to obtain the Gaussian distributions center about -75 ppm, -78 ppm, -83 ppm, and -89 ppm which are attributed, respectively, to Q0, Q1, Q2, and Q3 units [29, 30], while these multiple peaks were also deconvoluted for calculating the percentage of integral intensities of Qn. There are different features of Qn units at various hydration times. As the hydration process of C3S without calcium nitrate, the discrete SiO4 tetrahedral (Q0) in unhydrated C3S transformed to dimers Q1 and doubly coordinated tetrahedral Q2, following the increasing Q3. However, the Q0 and Q1 peaks keep the lowest level particularly at 28 days of the C3S hydration, while the Q2 fraction has been becoming a predominant level and Q3 fraction comes second. As the hydration process of C3S, the development of Q2 fraction is anticorrelated with that of Q1.In the case of calcium nitrate, theQ2 peak has been playing a dominant role in the dreierketten silicate chain structure until 3-day hydration, while the fraction for the Q3 peak is increased by calcium nitrate compared to the control group. Q2/Q1 ratios of hydrated C3S with calcium nitrate outweigh those of the control group, especially at an early age. The presence of calcium nitrate in the hydrated C3S generates a significant increase in the Q2/Q1 ratios at an early age. Calcium nitrate is clearly indicated to accelerate the degree of polymerization of the silicate chains in C-S-H gel considerably at an early age. More Q2 and Q3 peaks of the calcium nitrate group make the Q2/Q1 ratios rise significantly at an early age in agreement with the above studies of the DSC analysis of hydrated C3S in the presence of calcium nitrate.


## 3.1. Calorimetry

Figure1 shows the isothermal calorimetry data for C3S hydrated with calcium nitrate prepared under different liquid-to-solid ratio (L/S). Without the addition of calcium nitrate, the height of the early rate peak of C3S paste with L/S=0.5 increases, and the launch of the accelerating period is earlier. Commonly, the early hydration rate of C3S paste with L/S=0.5 develops more quickly than that of L/S=0.4; however, the presence of calcium nitrate is opposite due to more nucleation sites in C3S paste. The addition of calcium nitrate has a significant accelerating effect. When calcium nitrate is absent, the accelerating effect is greater under L/S=0.4 compared with L/S=0.5. But the addition of calcium nitrate makes the induction period slightly eliminate. Calcium nitrate can prompt the homogeneous nucleation [17] since the high abundance of Ca2+ in the pore solution combined with silicate ions dissolved from C3S. The early hydration of C3S paste is accelerated by calcium nitrate, which provides the development of pore structure and hydration products of C3S paste.Figure 1
Isothermal calorimetry of C3S pastes with different L/S and calcium nitrate.


## 3.2. N2 Sorption

According to the IUPAC classification, the hysteresis loops for all isotherms obtained from C3S samples are not of Type IV but of Type H3 due to no indication of a plateau at high P/P0 in Figure 2. Each adsorption branch has the similar feature of the typical Type II without limiting adsorption at high P/P0, and the desorption branch exhibits a different path before reaching a critical P/P0, which implies aggregates of plate-like particles resulting in slit-shaped pores. The C3S pastes for hydrating 3 and 7 days in Figure 2(a) have a narrower width of the hysteresis loop, while that of 28 days has the largest. However, the presence of calcium nitrate expands the hysteresis loop since hydrating for 3 days.Figure 2
Physisorption isotherms for C3S pastes with different hydration times in the (a) absence and (b) presence of calcium nitrate.
(a)
(b)The specific surface area results are shown in Table1. Since the Langmuir method is based on monolayer adsorption, the values for the Langmuir area are generally higher than those for the BET area. The specific surface area of C3S pastes is enhanced with an increase of hydration times whether the existence of calcium nitrate is included or excluded. However, the presence of calcium nitrate can increase the specific surface area of C3S paste. C3S can react quickly with water to form an amorphous phase, calcium silicate hydrates (C-S-H) with many gel pores, and calcium nitrate can accelerate the hydration of C3S resulting in the increasing specific surface area.Table 1
Specific surface area of C3S pastes with different hydration times (m2/g).
Sample
C3S 3 d
C3S 7 d
C3S 28 d
CN 3 d
CN 7 d
CN 28 d
BET area
9.16
11.29
33.52
15.89
25.95
38.52
Langmuir area
12.92
16.26
47.19
22.88
37.59
54.71For comparison purposes, the pore size distributions (PSD) are of very great significance as shown in Figure3. Pore size distributions are calculated by the Kelvin equation ranging from 2 to 50 nm. The mesopores in all samples are assessed by N2 sorption locating primarily at around 3.5 nm, while the gel pores cannot be addressed due to porewidths<2nm. However, the addition of calcium nitrate makes the pore width shift slightly up to about 4 nm with the increasing hydration time. These mesopores smaller than 50 nm play an important part in drying shrinkage and creep.Figure 3
BJH desorption PSD comparison for C3S pastes in the (a) absence and (b) presence of calcium nitrate.
(a)
(b)


## 3.3. STXM Analysis

As mentioned above, the development of the hydration products of C3S paste is also affected by calcium nitrate. Figure4 shows the XRD patterns of triclinic C3S and hydrated C3S pastes with calcium nitrate. In the presence of calcium nitrate, unhydrated C3S remains slightly at 7-day hydration since the reactivity of triclinic C3S is lower than monoclinic C3S. The feature peaks of portlandite are occurring at 1-day hydration of C3S pastes, while the morphology of portlandite presented the plate-like crystals surrounded by unhydrated C3S and C-S-H gel as shown in Figure 5.Figure 4
XRD patterns of triclinic C3S and C3S pastes with calcium nitrate.Figure 5
SEM images of 1-day hydration of C3S paste with calcium nitrate.Figure6 presents the single image of 1 d hydrated C3S taken at 340 eV (Figure 6(a)) and Ca L3,2-edge NEXAFS spectra (Figure 6(c)) of a selected area in Figure 6(a). Based on previous studies [18], the Ca L3,2-edge NEXAFS spectra of Ca(OH)2, anhydrous C3S, and pure C-S-H (in 17 d hydrated C3S) were investigated, respectively, in ways of STXM with NEXAFS in Figure 6(a). Each of these spectra is unique in terms of the peak shape, positions, and the energy splitting, which has been used as a fingerprint for identifications and investigations of Ca structure. Ca L3,2-edge NEXAFS spectra provide calcium coordination environment and characterize conveniently amorphous and crystalline Ca-containing materials.Figure 6
STXM results of 1 d hydrated C3S with calcium nitrate: (a) single image taken at 340 eV, (b) RGB overlay maps using SVD based on NEXAFS spectra of Ref. [18], (c) Ca L3,2-edge NEXAFS spectra of selected areas in (a).
(a)
(b)
(c)
(d)The observed multiple peak patterns of CaL3,2-edge NEXAFS spectra consist of two main spin-orbit-related peaks (a2 and b2) corresponding, respectively, to L3 and L2, along with several smaller peaks (a1 and b1) leading to the main peaks [19] (Figure 6(a)). The experimental resolution for the spectra is approximately less than 0.1 eV. The magnitudes and symmetry of the crystal field of calcium in the first coordination sphere result in crystal field splitting, which is the origin of this multipeak pattern [20]. The peak positions and energy separation values (ΔL3a2‐a1 and ΔL2b2‐b1) are associated with the symmetry of Ca-O sheet in C-S-H structure.CaL3,2-edge NEXAFS spectra of a selected area in Figure 6(c) show the different peak shapes, peak positions, and energy separations. Ca L3,2-edge NEXAFS for Areas 1, 2, 6, and 8 has the splitting energy with 1.3 and 1.2 eV for a2‐a1 and b2‐b1 and peak intensity ratios between a1/a2 and b1/b2 in agreement with the results of anhydrous C3S. Well-developed crystalline Ca(OH)2 with the largest splitting energy values and peak intensity ratios [18] are shown in Figure 6(a). Moreover, Bae et al. [18] investigated the 17 d hydrated C3S paste with water-to-solid ratio of 10 and concluded that the C-S-H of 17 d hydrated C3S has a very similar local structure around Ca but has less crystallinity comparing to synthetic C-S-H. Ca L3,2-edge NEXAFS spectra of C-S-H have energy separation 1.1 and 1 eV for a2‐a1 and b2‐b1 and the lowest peak intensity ratios [18], while the energy separation of 1.1 and 1.1 eV of Areas 3, 5, and 7 in one particle of 1 d hydrated C3S with calcium nitrate has the lowest peak intensity ratios. Therefore, calcium nitrate does not change the asymmetric 7-fold coordination of calcium in the calcium silicate hydrate (C-S-H), the primary hydration product.RGB overlay maps using Singular Value Decomposition (SVD) based on NEXAFS spectra obtained previously from Ref. [18] of Ca(OH)2, C-S-H, and anhydrous C3S are shown in Figure 6(a). Since various chemical components have unique features for NEXAFS spectra, the reference spectra obtained from known components were used to differentiate and visualize phases in a sample [21]. It was observed in the C3S particles under calcium nitrate solution that there are many magenta pixels (M = R + B = Ca(OH)2+unhydrated C3S) at the center in Figure 6(d) indicating that the unhydrated C3S in those pixels is transforming to crystalline Ca(OH)2. There are, however, a few cyan pixels (C = G + B = C-S-H+unhydrated C3S) at the boundary indicating that unhydrated C3S in that pixel is transforming to C-S-H, but there are few yellow pixels (Y = R + G = Ca(OH)2+C-S-H). Under the addition of calcium nitrate, the amorphous C-S-H surrounds the unhydrated C3S. However, portlandite is partly in transformation in Figure 6(d), while the formation of Ca(OH)2 partly occurs in Figure 5. Ca(NO3)2 can lower the amount of calcium hydroxide (CH) in hydrated cement pastes [6]. On the other hand, Ca2+ is the top diffusivity of cations, while NO3- is located at penultimate order, ranked in order of the effectiveness as accelerators [22–24]. Therefore, calcium nitrate can accelerate the hydration of C3S to some extent, but it is not the most effective one, such as CaCl2.


## 3.4.29Si MAS NMR Analysis

29Si MAS NMR plots for hydrated C3S with different hydration times in the absence or presence of Ca(NO3)2 are shown in Figure 7, and the results of the associated spectral deconvolutions are presented in Table 2. The connectivity of SiO4 tetrahedra, Qn, is used to describe various types of monomer, dimer, trimer, and tetramer, where n represents the number of bridging oxygens (Si-O-Si): Q0 site is isolated SiO4 tetrahedra, Q1 is SiO4 tetrahedra present in end units of a silicate chain, Q2 is a middle group, Q3 is a branching site, and Q4 sites link to four other SiO4 tetrahedra in a three-dimensional network. Amorphous C-S-H initially contains mainly dimeric silicate [25–27], while C3S includes nine inequivalent SiO4 tetrahedra (Q0 sites) between -69 ppm and -75 ppm [28].Figure 7
29Si MAS NMR spectra of C3S pastes as a function of hydration time in the (a) absence and in the (c) presence of calcium nitrate and deconvoluted spectrum for 28 d hydrate sample in the (b) absence and in the (d) presence of calcium nitrate.
(a)
(b)
(c)
(d)Table 2
29Si MAS NMR analysis for hydrated C3S paste at 25°C for hydration period of 1, 3, 7, and 28 days.
Samples
Percentage of integral intensities ofQn (%)
Q2/Q1
Q0-74 ppm
Q1-78 ppm
Q2-83 ppm
Q3-89 ppm
C3S_1 d
33.2
64.4
2.4
—
0.04
C3S_3 d
20.7
43.2
30.6
5.5
0.71
C3S_7 d
11.5
37.2
43.9
7.4
1.18
C3S_28 d
11.9
14.4
53.8
20.0
3.74
C3S+Ca(NO3)2_1 d
15.2
36.1
40.1
8.6
1.11
C3S+Ca(NO3)2_3 d
6.5
34.1
46.5
12.9
1.37
C3S+Ca(NO3)2_7 d
1.0
38.7
37.3
23.0
0.97
C3S+Ca(NO3)2_28 d
3.7
22.3
52.6
21.4
2.36In Figure7, 29Si MAS NMR spectra were fitted by the Gaussian functions to obtain the Gaussian distributions center about -75 ppm, -78 ppm, -83 ppm, and -89 ppm which are attributed, respectively, to Q0, Q1, Q2, and Q3 units [29, 30], while these multiple peaks were also deconvoluted for calculating the percentage of integral intensities of Qn. There are different features of Qn units at various hydration times. As the hydration process of C3S without calcium nitrate, the discrete SiO4 tetrahedral (Q0) in unhydrated C3S transformed to dimers Q1 and doubly coordinated tetrahedral Q2, following the increasing Q3. However, the Q0 and Q1 peaks keep the lowest level particularly at 28 days of the C3S hydration, while the Q2 fraction has been becoming a predominant level and Q3 fraction comes second. As the hydration process of C3S, the development of Q2 fraction is anticorrelated with that of Q1.In the case of calcium nitrate, theQ2 peak has been playing a dominant role in the dreierketten silicate chain structure until 3-day hydration, while the fraction for the Q3 peak is increased by calcium nitrate compared to the control group. Q2/Q1 ratios of hydrated C3S with calcium nitrate outweigh those of the control group, especially at an early age. The presence of calcium nitrate in the hydrated C3S generates a significant increase in the Q2/Q1 ratios at an early age. Calcium nitrate is clearly indicated to accelerate the degree of polymerization of the silicate chains in C-S-H gel considerably at an early age. More Q2 and Q3 peaks of the calcium nitrate group make the Q2/Q1 ratios rise significantly at an early age in agreement with the above studies of the DSC analysis of hydrated C3S in the presence of calcium nitrate.


## 4. Conclusions

In this study, we investigated the effect of calcium nitrate on hydration and pore structure of tricalcium silicate in ways of DSC, N2 sorption, STXM with NEXAFS, and 29Si MAS NMR. Calcium nitrate can accelerate the hydration of C3S to some extent and polymerization of the silicate chains within C-S-H considerably at an early age, resulting in the increased specific surface area.At 1-day hydrated C3S in the presence of calcium nitrate, amorphous C-S-H and crystalline portlandite surround the unhydrated C3S. Moreover, it is indicated from STXM combined with NEXAFS that the crystal phase, Ca(OH)2, is still partly in transformation at 1-day hydration of C3S with calcium nitrate. As for the atomic structure of C-S-H at 1-day hydrated C3S pastes, calcium nitrate does not change the asymmetric 7-fold coordination of calcium in the calcium silicate hydrate (C-S-H), the primary hydration product.These findings definitely validate the STXM with NEXAFS spectra as a significantly powerful tool for the investigation of the microstructure of the cementitious pastes to open the possibility of studying the in situ nanostructure of cementitious materials during hydration.



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*Source: 8419130-2020-04-22.xml*