Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 2316−2326 pubs.acs.org/journal/ascecg

The Hydration of β- and α′H‑Dicalcium Silicates: An X‑ray

Spectromicroscopic Study
Jiaqi Li,† Guoqing Geng,*,†,‡ Wenxin Zhang,† Young-Sang Yu,§ David A. Shapiro,§
and Paulo J. M. Monteiro†
†
Department of Civil and Environmental Engineering, University of California, Berkeley, 725 Davis Hall, Berkeley, California 94720,
United States
‡
Laboratory for Waste Management, OHLD/004, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
§
Advanced Light Source, Lawrence Berkeley National Laboratory, Building 2, 0437, Berkeley, California 94720, United States
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*
S Supporting Information

ABSTRACT: Dicalcium silicate (C2S) is an important clinker mineral in Portland

and belite-calcium sulfoaluminate cement. However, there is still a lack of
information on the local degree of silicate polymerization and calcium coordination
in C2S hydration products. This study aimed to fill this gap by characterizing the
hydration of two C2S polymorphs, the β- and α′H- types, using scanning transmission
X-ray microscopy coupled with ptychographic imaging. The results showed that the
coordination of the Ca species in β- and α′H-C2S had a distorted, cubic-like
symmetry, whereas the Ca coordination of calcium silicate hydrate (C-S-H), the main
hydration product, was structurally similar to that of tobermorite. The outer
hydration product (Op) of both polymorphs exhibited an increasing degree of silicate
polymerization over time. The inner hydration product (Ip) of β-C2S polymerized
slower than Op; however, the degree of silicate polymerization of both Ip and Op in
the α′H-C2S hydration system was comparable. The polymerization degree of Op was
relatively heterogeneous, whereas, in α′H-C2S, the polymerization degree was more homogeneous. Ptychographic imaging
shows that the Op of α′H-C2S exhibits coarser fibrils than the Op of β-C2S, and a clear Op−Ip interface of hydrated β-C2S is
observed.
KEYWORDS: Portland cement, Dicalcium silicate, Low carbon cement, Silicate chain polymerization, Calcium silicate hydrate,
Calcium coordination, Morphology

■ INTRODUCTION emission and energy consumption by 30% and 20%,

Concrete is the second most consumed material after water. 1 respectively.5
Its strength comes from the hydration of cement. The The main binding phase of hardened PC pastes and
production of conventional Portland cement (PC) accounts concretes is a calcium silicate hydrate (C-S-H) gel. The
for 8−9% of global CO2 emission and 2−3% of energy structure and properties of C-S-H govern the mechanical
consumption.2 The major compounds of PC clinker are properties and durability of PC-based materials.6,7 The well-
tricalcium silicate (Ca3SiO5, also termed C3S in cement accepted molecular models of C-S-H (Figure 1) are created by
chemistry notation), dicalcium silicate (Ca2SiO4, also termed modifying a tobermorite structure8 with defected dreierketten-
C2S; or belite as impure C2S), tricalcium aluminate (Ca3- type silicate chains, which are composed of bridging and
Al2O6), and tetracalcium aluminoferrite (Ca2AlFeO5). Among pairing tetrahedra, flanked on CaO7 sheets to form the calcium
them, C3S is the most abundant phase, but it has the highest silicate basal layer. The neighboring basal layers are separated
environmental impact due to the high calcination temperatures by zeolitic calcium ions and water.9 The structures of synthetic
and heavy CO2 emission from decomposing limestone. The nanocrystalline C-S-Hs have been extensively studied at the
cement industry is under increasing pressure to reduce CO2 atomic, molecular, and nano scales. However, the atomic and
emissions and energy consumption. Production of C2S-rich PC molecular structures (e.g., Ca and Si coordination) of
at the expense of the typically more abundant C3S is one way hydration product C-S-H have been inadequately studied
to lower the environmental impact of PC manufacturing.3 For due to their poor ordering along the c-axis. Understanding the
example, belite-calcium sulfoaluminate (BCSA) cement is a
very promising alternative to PC because the calcination Received: October 2, 2018
temperature of BCSA is 200 °C lower than PC.4 BCSA cement Revised: November 18, 2018
(also belite-rich) manufacturing is capable of reducing CO2 Published: December 20, 2018

© 2018 American Chemical Society 2316 DOI: 10.1021/acssuschemeng.8b05060

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composite materials with a heterogeneous microstructure. It

simultaneously provides morphological information and X-ray
absorption near-edge structure (XANES) spectra of the
elements of interest,34,35with a spatial resolution of up to 10
nm and a spectral resolution of 0.1 eV.36 C-S-H gel is
vulnerable to electron beam damage,37 and the soft X-ray used
in STXM (<2000 eV) is more likely to preserve the
morphology of C-S-H.38 The application of STXM in cement
research started in recent years;39−45 however, no STXM or
XANES study has been reported on the hydration of C2S.
In this work, the hydration products of C2S polymorphs (β-
and α′H-) were studied by STXM at the Ca L2,3- and Si K-
edges. The coordination of Ca of anhydrous C2S and C-S-H
was also analyzed. Silicate polymerization of the Op and Ip and
their C2S interfaces at two different ages were locally probed.
Ptychographic imaging was used to provide the interface
morphology between the Ip and Op and between water and
Figure 1. Schematic representation of the nanostructures of C-S-H. the Op with a spatial resolution of 10 nm.
The brown circles represent Ca species in the Ca-O sheet, and blue
triangles are silicate units in paired and bridging sites. The gray
diamonds and yellow squares represent sites which can be occupied ■ MATERIALS AND METHODS
by cations that charge-neutralize the structure as a whole (e.g., Ca2+ Preparation of β- and α′H-C2S. Chemical analytical grade
and/or K+). CaCO3, SiO2, and K2CO3 were mixed according to the stoichiometric
composition of 1.80CaO-0.10K2O-SiO2 to prepare monoclinic β-C2S.
The mixed powder was calcined at 1500 °C for 3 h and then cooled in
structure and properties of C-S-H is essential for optimizing air.46 Chemical analytical grade Ca2SiO4 and Ca3(PO4)2 were
the properties of sustainable cement-based materials. stoichiometrically mixed as 1.946CaO-0.892SiO2-0.054P2O5 to
The hydration of C2S is similar to the intensively studied prepare α′H-C2S. The mixed powder was sintered at 1450 °C for 6
hydration of C3S; both yield C-S-H gel and portlandite h, followed by air cooling.47 Note that, to ensure the fast formation of
(Ca(OH)2) as hydration products.10 β-C2S is the most a single phase (high purity) of β- and α′H-C2S, the calcination
temperatures of this laboratory synthesis were higher than typical
common polymorph of C2S in cements. Using the original calcination temperature of belite-rich cement (e.g., 1250 °C). The
surface of the unreacted particle as a reference, C-S-H exhibits C2S pellets were then ground into powders. The particle size
a distinct morphology in the outer and inner regions. The distribution D-values, D10, D50, and D90 of anhydrous β-C2S were
inner product (Ip) C-S-H from β-C2S hydration is spherulite- 1.19 μm, 6.74 μm, and 18.48 μm, respectively. The D10, D50, and
like on the nanoscale,11 while the outer product (Op) C-S-H is D90 of anhydrous α′H-C2S were 1.45 μm, 7.05 μm, and 19.08 μm,
fibrillar12 and contributes to the binding properties. Apart from respectively.
the apparent morphological difference due to the available Sample Preparation for STXM. Anhydrous C2S powders were
space for stacking,11 there is no significant difference in mixed with deionized water with a water-to-solid ratio (w/s) of 10 so
composition between the Ip and Op.12 The reactivity of β-C2S that the particles were easily isolated by drop-casting to satisfy the
transmission observation in the STXM. The suspensions were stored
is lower than that of C3S, but the β-C2S hydration is significant
in polyethylene tubes filled with N2 gas at 25 ± 1 °C. At early and late
for the long-term performance of PC concrete.13 The β-C2S curing ages (10 days and 40 days for α′H-C2S; 17 days and 51 days for
hydration has been investigated by nuclear magnetic resonance β-C2S), the suspension of 0.5 μL was dropped onto a Si wafer frame
(NMR),14−17 electron microscopy,18−20 and other spectros- (5 mm × 5 mm, 100 μm thick), where a 100 nm thick Si3N4
copies.21−24 However, these techniques are not capable of membrane window (1 mm × 1 mm, 100 nm thick) is in the center.
locally probing the polymerization degree of the silicate chain The liquid was quickly and gently absorbed with a tip of KimWipes
of the Ip or Op; e.g., NMR, Raman spectroscopy, and infrared from the edge of the Si frame. The liquid removal process was
spectroscopy can provide chemical environmental Si of C-S-H, monitored under an optical microscope to ensure that most of the
but are not capable of providing adequate spatial data.25−27 solids remain on the membrane window. The anhydrous powders
Scanning electron microscopy provides high-resolution images, were dry-dusted on the Si3N4 membrane windows directly. These
windows were then placed on the STXM sample stage inside a
whereas the polymerization degree of C-S-H cannot be vacuum chamber.
evaluated.28 The potential artifacts generated by the harsh Scanning Transmission X-ray Microscopy. The XANES
vacuum and high energy electron beam are also not completely spectra and images at Si K-edge (1830−1880 eV) and Ca L2,3-edge
understood.29−31 Recently, α′H-C2S, another polymorph of (342−360 eV) were obtained at beamlines 5.3.2.1 and 5.3.2.2,
C2S, has increasingly gained research and industrial interests respectively, at the Advanced Light Source of the Lawrence Berkeley
due to its higher hydration reactivity compared to β-C2S.32 National Laboratory (LBNL). Comprehensive descriptions of the
However, the current understanding of the microchemistry STXM beamlines are given in refs 36 and 48.
(e.g., local coordination environment and silicate polymer- The optical density (OD) at a specific energy of all pixels is affected
ization) during its hydration is limited.33 Understanding the by composition, density, and sample thickness.40 Element mappings
were obtained by differential measurements of the OD at pre- and on-
hydration of C2S polymorphs and the structure of their
edge at a spatial resolution up to 25 nm. Image stacks were collected
hydration products C-S-H is essential for optimizing the by scanning the region of interest (ROI) at a series of beam energies,
properties of sustainable cement and concrete and for lowering which yielded a XANES spectrum of each pixel on the ROI. RGB
the CO2 emission and energy use in the construction industry. overlay maps, which visualize multiple phases with various
Scanning transmission X-ray microscopy (STXM) is a compositions, were generated using singular value decomposition
powerful technique for characterizing the microchemistry of with reference spectra. All data processing was conducted using

2317 DOI: 10.1021/acssuschemeng.8b05060

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Figure 2. Hydrated β-C2S at 17 days: (A) Transmission image of the ROI taken at 349 eV; (B) selected regions in the Ca element map for the
XANES spectra; (C) Ca L2,3-edge XANES spectra extracted from different regions specified in (B).

aXis2000 software.48 At each age, at least two RGB maps were taken Ca−O bond lengths for Ca2 range from 2.400 to 2.676 Å with
to obtain statistically reliable results, and at least 10 spectroscopic an average of 2.503 Å. The complex coordination of Ca1 and
measurements were taken from different particles on each Si3N4 Ca2 in β-C2S produces weak cubic-like crystal field splitting
membrane.
effects.
Ptychographic images were collected at 800 eV at beamline 5.3.2.1.
Full details of the imaging technique are given in ref 44. The spatial To avoid X-ray absorption saturation at low energy, only
resolution of these transmission images is ∼10 nm. The images were particles with a size of ∼1 μm (Figure 2A, B) were measured at
reconstructed by the Nanosurveyor package.49 The width of C-S-H Ca L2,3-edge. The 17-day hydrated β-C2S grains at the Ca L2,3-
fibers of hydrated samples in the ptychographic images was quantified edge show mostly identical peak positions and an equivalent
using ImageJ with F3D plugin developed at LBNL.50 splitting energy in each grain, indicating that the Ca in each
grain exhibits a similar environment. Peaks a2 and b2 in the
■ RESULTS AND DISCUSSION selected areas are 0.1 eV lower than anhydrous β-C2S,
Ca Coordination of Anhydrous β-C2S and Hydrated β- suggesting a lower bond strength of Ca−O. The splitting
C2S for 17 days. The Ca L2,3-edge XANES spectra (Figure 2) energies in the selected areas are 1.1 eV, suggesting a distorted
consist of two major peaks, L3 2P3/2 (a2) and L2 2P1/2 (b2), octahedral-like symmetry for Ca.52 The X-ray absorption
which are due to the loss of degeneracy of 2p orbitals by spin− features (i.e., splitting energy and peak positions) are similar to
orbital interactions,51 along with a number of minor leading 14 Å tobermorite (calcium silicate hydrate mineral, [Ca4Si6-
peaks, a0, a1, and b1, in order of increasing energy. The peak O16(OH)2·2H2O]·(Ca·5H2O)),57,58 suggesting the C-S-H
energy difference of a2−a1 and b2−b1 (ΔL3 and ΔL2, termed as formed in this hydration system is structurally analogous to
splitting energy) and the intensity of the minor peaks are tobermorite. The relative intensity ratios of peak a1-to-a2
relevant to the coordination symmetry of Ca in the first shell (I(a1)/I(a2)) and b1-to-b2 (I(b1)/I(b2)) of these selected
and its ordering.52−55 areas are 0.021−0.041 and 0.050−0.077, respectively, which
The Ca L2,3-edge XANES spectrum (Figure 2C) of are lower than hydrothermally synthetic C-S-H at 25 °C
anhydrous β-C2S (monoclinic) exhibits a cubic-like symmetry (0.05−0.15 for I(a1)/I(a2) and 0.07−0.15 for I(b1)/I(b2)).38
with peak a1o located between a1 and a2, and the peak energy The details in the calculation of relative intensity of these peaks
differences of a2−a1 and b2−b1 are 1.54 and 1.2 eV, are shown in Figure S2 (Supporting Information). Synthetic C-
respectively. β-C2S contains seven-fold and eight-fold coordi- S-H has a longer range order than C-S-H formed in the β-C2S
nated Ca, denoted as Ca1 and Ca2 (Supporting Information, hydration along the c-axis.59 This suggests a shorter range
Figure S1). The equatorial plane of Ca1 is parallel to (101̅) order for Ca in this hydration system since the Ca/Si molar
with Ca−O bond lengths for Ca1 ranging from 2.273 to 2.892 ratio of C-S-H in hydrated β-C2S ranges from 1.2 to 2.1.60
Å with an average of 2.528 Å.56 The five equatorial O atoms Moreover, no contribution by portlandite (a non-strength-
are not exactly coplanar. The Ca2 is coordinated by eight O giving phase in hydrated C2S) was observed in the spectra,
atoms with a distorted symmetry for the cube, where the two suggesting that C-S-H does not intermix with portlandite at the
trapezoids formed of the top four and bottom four O atoms are 25 nm scale in this ROI, and the interlayer six-fold coordinated
misaligned along each other’s diagonal direction by 55°. The Ca is also distorted. Thus, the Ca of C-S-H in hydrated β-C2S
2318 DOI: 10.1021/acssuschemeng.8b05060
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Figure 3. Hydrated α′H-C2S at 10 days: (A) Transmission image of the ROI taken at 349 eV; (B) selected regions in the Ca element map for the
XANES spectra; (C) Ca L2,3-edge XANES spectra extracted from different regions specified in (B).

is short-range-ordered and tobermorite-like. Portlandite symmetry (less distorted) than in β-C2S. For Ca1 in β-C2S, its
crystallites were observed elsewhere in these dilute systems coordination number is seven, which is incapable of providing
(Supporting Information, Figure S3). an ideal cubic symmetry.
Hydrated C3S at 17 days also exhibited comparable peak Portlandite was not observed in this region for α′H-C2S
positions, splitting energies, and intensity ratios in XANES at hydrated for 10 days. Mostly identical peak positions and peak
the Ca L2,3-edge,61 indicating that the Ca environment of intensities were observed in each grain. Peaks a2 and b2 in the
hydrated C3S is similar to that of hydrated β-C2S. The selected areas are ∼0.1 eV lower than for α′H-C2S, and the
extended X-ray absorption fine structure study showed that the peak positions are 0.05 eV higher than for hydrated β-C2S. The
Ca-O environment of hydrated β-C2S is similar to that of 11 Å splitting energies in the compounds are ∼0.1 eV lower than for
tobermorite, but the coordination number and Ca−O bond α′H-C2S but ∼0.05 eV higher than for hydrated β-C2S. This
length of C-S-H could not be determined due to the presence suggests that the bond strength of Ca−O of hydrated α′H-C2S
of portlandite.62 An 17O NMR study demonstrated that Ca- is slightly higher than that for hydrated β-C2S; namely, more
OH sites are present in C-S-H of hydrated β-C2S.17 The C-S-H six-fold coordinated Ca is present in the α′H-C2S hydration
structure of hydrated β-C2S proposed by Richardson12 system. The intensity ratios of hydrated α′H-C2S are 0.018−
contains six- and seven-fold coordinated Ca in the interlayer 0.038 and 0.037−0.067, which are also lower than for
and intralayer, respectively. The model proposed by Gartner63
anhydrous but comparable to or slightly lower than hydrated
suggests that the interlayer Ca of C-S-H from hydration of C3S
β-C2S. These absorption features indicate that the coordina-
and β-C2S is six-fold coordinated. In the present work, the
tion symmetry of Ca in hydrated α′H-C2S is also tobermorite-
distorted six-fold Ca in the interlayer of hydrated β-C2S fits
like, but the ordering of Ca is slightly lower than for hydrated
both models.
Ca Coordination of Anhydrous α′H-C2S and α′H-C2S β-C2S.
Hydrated for 10 Days. The Ca L2,3-edge XANES spectra of Si Environment of Anhydrous β-C2S and β-C2S
α′H-C2S (orthorhombic) also exhibits a cubic-like symmetry Hydrated for 17 Days. The major peak of a1 at the Si K-
with peak energy differences of a2−a1 of 1.57 eV and b2−b1 of edge of β-C2S (Figure 4C) is assigned to the electronic
1.25 eV in Figure 3. This indicates a slightly stronger crystal excitation from 1s to the antibonding 3p-like state orbital (t2)
field of Ca for α′H-C2S. α′H-C2S contains nine- and eight-fold of tetrahedral Si.64,65 Pre-edge peak a0 is attributed to the
coordinated Ca at two sites (denoted as Ca1 and Ca2; see dipole-forbidden transition of 1s electrons to the antibonding
Figure S1 in the Supporting Information) with Ca−O bond 3s-like states.66 This forbidden peak appears due to the mixing
lengths for Ca1 ranging from 2.214 to 3.175 Å with an average of s- and p-states when the SiO4 tetrahedra coordination is
of 2.708 Å, and those for Ca2 ranging from 2.292 to 2.927 Å highly distorted. Thus, the intense a0 peak of β-C2S suggests a
with an average of 2.545 Å.56 The superposition of symmetries strong distortion of the silicate tetrahedron. The minor peak of
and complex coordination leads to the cubic-like crystal field a2 is assigned to the multiple-scattering effect from more
splitting of α′H-C2S. The energy difference in α′H-C2S is distant atom shells through a photoelectron interaction; its
slightly larger compared to β-C2S (monoclinic), suggesting energy is governed by the interatomic distance and structural
that Ca-O complexes in α′H-C2S are more similar to cubic-like complexity.67
2319 DOI: 10.1021/acssuschemeng.8b05060
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Figure 4. Hydrated β-C2S at 17 days: (A) Transmission image of the ROI taken at 1849 eV; (B) selected regions in the Si element map from the
XANES spectra; (C) Si K-edge XANES spectra extracted from different regions specified in (B); (D) RGB overlay map using XANES spectra
obtained from the C-S-H (Area 4, green) marked in (B) and reference spectrum of anhydrous β-C2S (red). More RGB over maps can be found in
Figure S4 (Supporting Information).

The interface between the β-C2S core and the hydrous layer bond length, rather than the polymerization degree, dominates
C-S-H is well distinguished (Figure 4), indicating changes in the Si K-edge shift.
the phase density. The OD of the hydration product layer The energy difference between a1 and a2, Δa2−a1, can be
slightly decreases with increasing distance from the interface, used to evaluate the degree of silicate polymerization.38,43,61,68
which is associated with several small brighter regions. The values of Δa2−a1 for areas 3 and 4 are equivalent,
Compared to the C3S hydration system,61 the C-S-H of suggesting that the degree of polymerization of the C-S-H here
hydrated β-C2S is more dispersed, and fibrils are not present at is comparable. The energy positions of multiple scattering
this age and at this resolution (Figure 4A). peaks (e.g., a2) are affected by the Si interatomic distances,
Peak a1 is not shown at ∼1851.1 eV in areas 3, 4, 6, but a while the intensity and number of resonances are heavily
single a1 peak is at 1848.8 eV in these areas (Figure 4C), dependent on the bond angle, site symmetry, and number of
suggesting that C-S-H is the only silicate phase in these areas. nearest neighboring oxygen atoms (Si in most cement phases
The absorption features of C-S-H in hydrated β-C2S resemble are four-fold coordinated, expect thaumasite, where Si is six-
those of C-S-H in C3S hydration systems.43,61,64 The Si K-edge fold coordinated).70 Two a2 peaks are distinguished in the
(a1 peak) at 1848.8 eV of C-S-H is 2.2 eV lower than that of β- spectra in areas 2 and 5. In these areas, a peak at 1848.8 eV and
C2S due to the longer Si−O bond of the C-S-H relative to β- a broad shoulder/hump at ∼1851.1 eV were observed. The
C2S.56,69 Li64 concluded that, although there is considerable peak is assigned to the a1 peak of C-S-H, and the shoulder/
overlapping for silicate minerals with different polymerization hump is the contribution of the a1 peak (at 1851.0 eV) of
types, the Si K-edge generally shifts to higher energy with anhydrous β-C2S. These absorption features suggest that areas
increased silicate polymerizations. Thus, in this case, the Si−O 2 and 5 are mixtures of C-S-H and anhydrous β-C2S, and the
2320 DOI: 10.1021/acssuschemeng.8b05060
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Figure 5. Hydrated β-C2S at 51 days: (A) Transmission image of the ROI at 1849 eV; (B) selected regions in the Si element map for the XANES
spectra; (C) Si K-edge XANES spectra extracted from different regions specified in (C); (D) ptychographic image of another area at the same age.
Op is indicated by blue arrows, Ip is indicated by red arrows, and portlandite is indicated by yellow arrows.

hydration here is incomplete. Similarly, areas 7 and 8 are mixes 1853−1854 eV73 since the basal layers of C-S-H are separated
of C-S-H and anhydrous β-C2S, implying that small β-C2S by [Ca(H2O)6]2+ or [Ca(OH)(H2O)5]+.63 29Si NMR studies
particles exist in these areas. This fact is consistent with the showed that the mean silicate chain lengths of C-S-H of 7−12
original granulometry result of β-C2S; ∼10% of β-C2S was months hydrated β-C2S are still lower than 3.5.12,74 This
below 1 μm. Note that a weak contribution of C-S-H to the suggests that the proportion of long silicate chains (octamer or
spectrum at ∼1848.8 eV is observed in area 1 since C-S-H longer) in this C-S-H is relatively low. Therefore, the C-S-H at
surrounds the entire grain. Δa2−a1 of area 6 is 0.9 eV lower 17 days is mainly a mixture of dimer and pentamer C-S-Hs.
than those of areas 3 and 4 (∼15.7 eV), suggesting a lower It is well-known that the degree of silicate polymerization of
degree of polymerization of C-S-H in the area. The difference synthetic C-S-H increases as Ca/Si decreases.26,27 Although
in local polymerization degree can be explained by the different the degree of polymerization of hydrated β-C2S progressively
dissolution rates on the crystal faces and by different numbers increases over time,17,75 there is no significant variation in the
of surface defects of β-C2S;71 multiple crystal faces with low mean Ca/Si of Op (excluding intermixed portlandite) with
hydraulic reactivity occur in area 6. Note that, hydraulic age.37 Thus, it is difficult to estimate the local degree of
reactivity of all faces of pure β-Ca2SiO4 is similar; the dopant polymerization based on Ca/Si ratio. STXM is a more reliable
changes the local reactivity of β-C2S crystals.72 Similarly, the technique to locally probe the variation in silicate polymer-
value of Δa2−a1 for C-S-H in area 9 is 0.7 eV lower than that ization of the C-S-H without considering intermixed micro-
for C-S-H in the unconstrained space. The RGB overlay map crystalline portlandite in the hydrous regions12 and unreacted
(Figure 4D) shows that the C-S-H surrounds the unreacted β-C2S.
core, which is consistent with the analysis above. The values of Si Environment of Hydrated β-C2S for 51 Days. Two
Δa2−a1 for C-S-H among different grains (Areas A−D) are distinct optical densities were observed at 51 days (Figure 5A).
15.6−16.1 eV, indicating a distinction in silicate polymer- Double a1 peaks are not observed in Figure 5B, and only a
ization due to the interference of other grains and the single a1 peak at 1848.9−1849.1 eV occurs. Peak a0 at 1847.9
hydration rate. In addition, the contribution of cross-linking eV was not observed, suggesting a fully hydrated grain (see
sites to the spectra is not observed in the typical range at Supporting Information, Figure S5). The peak difference of
2321 DOI: 10.1021/acssuschemeng.8b05060
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Figure 6. Hydrated α′H-C2S at 10 days: (A) Transmission image of the ROI taken at 1849 eV; (B) selected regions in the Si element map for the
XANES spectra; (C) Si K-edge XANES spectra extracted from different regions specified in (B); (D) RGB overlay map using XANES spectra
obtained from the C-S-H (Area 7, green) marked in (B) and reference spectrum of anhydrous α′H-C2S (red).

Δa2−a1 for areas 5, 6, 7, 8, 9, and B is 16.7−17.0 eV, and 15.8− partial replacement of divalent Ca by monovalent K from the
16.2 eV for areas 1, 2, 3, and 4; two distinct ranges of Δa2−a1 dopant.76 Future study will focus on the coordination
are observed in Figure 5C. Thus, the two distinct ODs indicate environment of K in this system and the electron density
the existence of Ip (dark region) and Op (light region) in around these atoms.
Figure 5A. Areas 5, 6, 7, 8, and 9 are Ip dominant, while the The ptychographic image (Figure 5D) shows the fibrillar Op
areas 1, 2, 3, and 4 are Op dominant. The Si K-edge (a1) and of another hydrated β-C2S particle at 51 days; the width of
Δa2−a1 of Ip are both lower compared to those of Op, fibers has a distribution of 11−25 nm, which is smaller than the
indicating a lower silicate polymerization and a slightly longer Op of C3S.77 The Ip of β-C2S exhibits a dense aggregated
Si−O bond for Ip. The Δa2−a1 and Si K-edge for Op at 51 structure, and the Ip of C3S with the same w/s exhibits a less
days are slightly higher than at 17 days, revealing that the Op dense structure with aggregates of globules.77 The morpho-
polymerizes over time. The lower Δa2−a1 for areas 10 and A logical difference between the two Ip’s can be explained by the
may be explained by impingement from adjacent grains. lower reactivity of β-C2S. Geng68 reported that the Ip and Op
Similarly, contribution of cross-linking sites to the spectra was of hydrated C3S exhibit an identical Si K-edge with a higher
also not observed due to the abundant interlayer Ca between energy for the a2 peaks of Op, showing that Ip has a lower
basal layers of C-S-H.63 Thus, both Op and Ip are likely degree of silicate polymerization. Portlandite microcrystallites
mixtures of dimer and pentamer C-S-Hs with very small intermixed with Op is observed, which is consistent with TEM
amounts of octamer and longer chains. The values of Δa2−a1 study of Richardson.11
for Op and Ip are larger compared to those of synthetic C-S-H Si Environment of Anhydrous and Hydrated α′H-C2S
with a bulk Ca/Si molar ratio of 1.4,38 suggesting that the for 10 Days. Similar to β-C2S, pre-edge peak a0 was also
electron shielding on Si from cations in hydration product C-S- observed in α′H-C2S (Figure 6C), suggesting a slight distortion
Hs is weaker. This can be explained by the highly distorted Ca of the silicate tetrahedron of α′H-C2S. The Si K-edge of α′H-
of [Ca(OH)(H2O)5]+ in the interlayer of C-S-Hs, and the C2S is 0.2 eV higher than for β-C2S, suggesting a slightly
2322 DOI: 10.1021/acssuschemeng.8b05060
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ACS Sustainable Chemistry & Engineering Research Article

Figure 7. Hydrated α′H-C2S at 40 days: (A) Transmission image of the ROI taken at 1849 eV; (B) selected regions in the Si element map for the
XANES spectra; (C) Si K-edge XANES spectra extracted from different regions specified in (B); (D) ptychographic image.

shorter Si−O bond for α′H-C2S compared with β-C2S, which is between different grains suggests that the polymerization is not
consistent with XRD refinement.56 obviously interfered by adjacent grains. Additionally, the C-S-
Similar to β-C2S hydration, the interface between non- Hs are mainly mixtures of dimer and pentamer units, and a
fibrillar Op and α′H-C2S was observed at 10 days (Figure 6). cross-linking effect was not observed on the spectra. Compared
The Si K-edge and Δa2−a1 of hydrated α′H-C2S at 10 days are to the Op of β-C2S at 51 days, hydrated α′H-C2S at 40 days
equivalent to or 0.2−0.3 eV larger than that for hydrated β-C2S
exhibited a comparable polymerization degree at an earlier age.
at 17 days. Thus, the chemical environment of Si in hydrated
This confirms the higher reactivity of α′H-C2S compared with
α′H-C2S is similar to that in β-C2S hydration at 17 days with a
comparable degree of polymerization at an earlier age. The β-C2S.
polymerization degree of the Op is more homogeneous since The ptychographic image (Figure 7D) shows the fibrillar C-
the Δa2−a1 values of all C-S-Hs here are ∼15.9 eV. Again, Op S-H with a width of 15−30 nm, which is larger than hydrated
cross-linking sites are not present, suggesting that the Op is still β-C2S but smaller than hydrated C3S (41−59 nm),77 and the
mainly a mixture of dimer and pentamer units.18 Thus, α′H- inner C-S-H exhibits a looser aggregated structure with ∼17
C2S exhibits a higher reactivity relative to β-C2S. This work is nm voids compared to the Ip of hydrated β-C2S. The Ip’s of
consistent with experimental and simulation studies on the hydrated β-C2S, C3S, and PC with a practical w/s (i.e., <0.6)
reactivity32,47,78 but provides new details on the rate of appear to be small and globular.79 The larger void of the Ip
polymerization of α′H-C2S hydration. relative to the Ip of hydrated C3S79 could be induced by the w/
Si Environment of Hydrated α′H-C2S for 40 Days. The s of 10 used in this study, which provides sufficient space for
C-S-H of α′H-C2S at 40 days is fibrillar in Figure 7. There was
nanocrystallite growth during the fast hydration. The micro-
no Ip/Op interface in the fully hydrated grain (see Supporting
Information, Figure S6) observed. The values of Δa2−a1 for all structure of hydrated α′H-C2S is similar to that of hydrated C3S
the areas range from 16.7 to 17.0 eV, suggesting a relatively with the same w/s77 instead of the hydrated β-C2S mentioned
homogeneous polymerization. This is a primary difference above. Thus, the morphological difference among the silicates
compared to β-C2S. The Si K-edge (a1) of all areas is in these diluted systems may be relevant to their hydration
comparable, suggesting similar Si coordination in these areas. reactivity. More ptychographic images can be found in Figure
The comparable degree of polymerization of the interfaces S7 (Supporting Information).
2323 DOI: 10.1021/acssuschemeng.8b05060
ACS Sustainable Chem. Eng. 2019, 7, 2316−2326
ACS Sustainable Chemistry & Engineering Research Article

CONCLUSIONS Author Contributions

■
The coordination environments of Ca and Si in anhydrous β- J.L., G.G., and P.J.M.M. conceived and designed the experi-
C2S, α′H-C2S, and their hydration products were studied using ments. J.L. conducted the experiments. Y.-S.Y. and D.A.S.
STXM; the morphology of C-S-Hs was imaged by ptychog- supported the imaging experiments. J.L., G.G., and W.Z.
raphy. The key conclusions are analyzed the results. J.L. and G.G. wrote the manuscript. All
authors reviewed the manuscript.
(1) Ca in both anhydrous phases are in a distorted cubic
symmetric coordination. The Ca coordination of C-S-H Notes
in both hydration systems is highly distorted and is The authors declare no competing financial interest.
similar to 14 Å tobermorite but have a shorter-range
order. More six-fold coordinated Ca occur in hydrated ■ ACKNOWLEDGMENTS
α′H-C2S than in hydrated β-C2S. This research was founded by the Republic of Singapore’s
(2) The Si of both anhydrous phases have asymmetric National Research Foundation through a grant to the Berkeley
tetrahedral coordination. The silicate chain of the Op in Education Alliance for Research in Singapore (BEARS) for the
both hydration systems polymerizes over time. The Singapore-Berkeley Building Efficiency and Sustainability in
hydration products in the α′H-C2S system polymerize the Tropics (SinBerBEST) Program. The Advanced Light
faster than in β-C2S. The hydraulic reactivity of α′H-C2S Source is supported by the Director, Office of Science, and
is higher. Office of Basic Energy Sciences of the U.S. Department of
(3) Ip has a lower degree of silicate polymerization than Op Energy under Contract No. DE-AC02-05CH11231. G.G. also
in fully hydrated β-C2S, which is accompanied by a wants to acknowledge European Union’s Horizon 2020
slightly longer Si−O bond due to the space constraint research and innovation programme under the Marie
for contacting water. Compared with hydrated β-C2S, Skłodowska-Curie grant agreement No. 701647. We thank
the silicate polymerization in hydrated α′H-C2S is more Matthew Marcus for insightful discussions on fitting and
homogeneous. interpretation of Ca L2,3-edge XANES spectra. We thank Ellis
(4) The C-S-H of hydrated β-C2S exhibits fine fibrils that Gartner for the personal communication and help on the study
intermix with portlandite, and Ip appears to be a dense of dicalcium silicates.
aggregated structure. The morphology of fully hydrated
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2326 DOI: 10.1021/acssuschemeng.8b05060

ACS Sustainable Chem. Eng. 2019, 7, 2316−2326