Cement and Concrete Research 159 (2022) 106858

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Cement and Concrete Research

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

Endowing strength to calcium silicate hydrate (C-S-H) powder by high

pressure mechanical compaction
Zhe Zhang, Yu Yan, Zhengyao Qu, Guoqing Geng *
Department of Civil and Environmental Engineering, National University of Singapore, 117576, Singapore

A R T I C L E I N F O A B S T R A C T

Keywords: The strength origin of C-S-H matrix is a key question in cement and concrete research, which remains largely
C-S-H unclear despite a century of study. Here we present a novel approach to endow strength integrity to C-S-H
High pressure mechanical compaction powders via mechanical compaction at room temperature. The unprecedented 2000 MPa compaction load results
Ca/Si ratio (C/S)
in a bulk C-S-H with tensile strength (~24 MPa) one order of magnitude higher than C-S-H matrix from hy­
RH condition
Mechanical properties
dration. This practice enables observations on how Ca/Si ratio (C/S) and initial moisture conditions affect their
overall mechanical properties (hardness and strength), which are correlated with the micro-structures studied by
1
H NMR and electronic microscope. We conclude that the bond between closely-contacted C-S-H particle, rather
than the total porosity, is key to the bulk strength. The bond is clearly weakened when excessive water exists
between C-S-H particles. This work provides novel insight to the strength origin of C-S-H.

1. Introduction how it is affected by the chemical and moisture composition of C-S-H. In

Calcium-silicate-hydrate (C-S-H) is the main binding phase in mod­
ern concrete [1]. It is a poorly crystalline analogue of tobermorite,
where layers of Ca are coordinated by silicate chains on both sides. The
stoichiometry of Ca-to-Si ratio (C/S) and H2O-to-Si ratio may vary in the
range of 0.7–2.3 and 0.5–3, respectively, accompanied by a change of
silicate chain linkage and interlayer spacing [2–7]. If the paste contains
siliceous and/or aluminous supplementary cementitious materials, the
mean value of Ca/(Si + Al) may reduce to less than one, meanwhile the
(aluminium) silicate chain increases in its continuity [8,9]. The bulk C-S-
H volume usually hosts water in three different forms: tightly-bound
water in the interlayer, condensed water in gel pores (2–8 nm) and
capillary pores (>8 nm) [10]. They can be completely or partially
removed through drying, accompanied by a variation in the properties
and micro-structures [11–13].
Of all the knowledge about C-S-H, the microscale origin of its me­
chanical properties has been a key focus in cement and concrete study
since the dawn of this research field. While the macroscale testing of
concrete strength has been standardized for decades, the microscale
characterization of the mechanical properties remains a challenge for C-
S-H as it is often intermixed with other phases, entangled in different
ways at different length scale [14–16] . A holistic picture of how C-S-H
responds to mechanical load at different scale is missing, not to mention
the last two decades, nano- and micro- indentation have been widely
used to test mechanical properties of pure C-S-H phase, e.g. hardness,
elastic modulus [15,17–19] and creep [20–22]. A few studies also re­
ported the micro-testing of compressive strength [23,24] and tensile/
flexural strength [25–27] of isolated C-S-H volume from the hydrated
paste using micro-fabrication tools. A widely accepted conclusion is that
the packing factor or intrinsic porosity of the C-S-H gel greatly influences
its mechanical properties [28,29].
Two types of C-S-H with distinct morphology and density have been
generally observed in the hydration paste of OPC, named inner product
(Ip) and outer product (Op). The Ip usually has a lower porosity and
consequently better mechanical properties than Op [15,17,30]. It is also
noticed that the property of C-S-H is highly dependent on scale effect.
For example, high pressure XRD reveals the bulk modulus of C-S-H to be
60–90 GPa [31–33] which is consistent with atomistic simulations
[31,34,35] but significantly larger than nano-indentation results (typi­
cally in the range of 10–20 GPa) [36–38]. The scale effect is even
stronger for strength of C-S-H. Recent studies, both experiments and
simulations, found that the tensile strength of components in cement
paste at small scale is much higher than the macroscopic tensile strength
of concrete which is usually <10 MPa. For instance, low and high
density C-S-H phases are predicted to have tensile strengths of 66 MPa
and 320 MPa, respectively, by means of inverse analysis using a multi-

* Corresponding author.
E-mail address: ceegg@nus.edu.sg (G. Geng).

https://doi.org/10.1016/j.cemconres.2022.106858
Received 30 December 2021; Received in revised form 15 May 2022; Accepted 29 May 2022
Available online 7 June 2022
0008-8846/© 2022 Elsevier Ltd. All rights reserved.
Z. Zhang et al.
scale model in cement pastes [39]. Micro-bending test revealed the
tensile strength of the hydrate phases to be in the range of 264 MPa (Op)
to 700 MPa (Ip and portlandite). The macro compressive strength of C-S-
H (~20 MPa [40–42]) were much smaller than that in micro scale
(>400 MPa [23,24]). It remains unclear how the multiscale structure
dominates the mechanical behaviour in various length scales.
Apart from the structural hierarchy and intermixture with other
phases, the intrinsic mechanical property of C-S-H cannot be unambig­
uously deciphered without a control of its chemical composition, such as
the C/S and moisture content. The influence of chemistry on the mo­
lecular configuration and nano-morphology of C-S-H has been well
studied in the past several decades [43–46], yet a theory that links the
change in chemistry and mechanical property is yet to be established. A
few studies observe some relationship between composition and me­
chanical properties. At atomic level, the elastic modulus of C-S-H in­
creases with increasing C/S according to the experimental results from
high-pressure XRD study [31,32]. Force field atomistic studies seem to
report controversial results. Some studies reported a decreasing trend of
elastic modulus along with the increase of C/S in the C-S-H model
[28,34], while others reported an opposite trend when C/S increases
from 0.8 to 1.5 [35]. This disagreement is likely due to the variation in
the C-S-H model and the force field used, which again awaits validation
using more experiment data. At nano or micro scale, indentation study
reveals that elastic modulus of C-S-H made of a mixture of particles
increases when the Ca/Si molar ratio decreases [36]. To settle the
dispute, more detailed experimental and simulation work on synthetic
single-phase C-S-H is needed.
Nonetheless, an agreement seems to have been reached that the
mechanical behaviour of C-S-H reveals a nano-granular nature, although
there is an ongoing debate on the size, shape, and even the existence of a
representative ‘grain’ of C-S-H at nanoscale [22,47–50]. The overall
mechanical response of C-S-H is thus postulated to be controlled by how
the grains interact with each other (e.g., their cohesion and friction) and
how each grain responses to load [8,51]. It was proposed that a sub­
stantial portion of the cement paste cohesion sources from the short- and
medium-range surface forces mediated by partially or totally hydrated
calcium ions [8] This framework is useful in explaining the elastic
modulus [17,50], drying shrinkage [52,53], and creep [20,21] of
cement paste, yet not reported on the origin of the strength integrity of
C-S-H.
In this study, we attempt to generate C-S-H pellets with macro-scale
strength integrity from loosely packed powders produced by hydro­
thermal reaction. Through this practise, we aim to find out how strength
originates when C-S-H grains are mechanically forced to contact each
other (a process referred to as ‘high pressure mechanical compaction’
[54]). To investigate the effect of chemical conditions to the strength of
compacted C-S-H pellets, we started from powders of controlled C/S and
moisture conditions. Pore structures, i.e. interlayer, gel and capillary
porosity of C-S-H pellets were quantified as a function of the compres­
sion load. Strength of the pellets was characterized by micro-
indentation, macro-indentation and splitting tensile test, which were
used to discuss the multiscale effect of its mechanical property. For the
first time, we reported a bulk C-S-H with almost no hierarchy in pore
structure, resulting in a macroscale splitting tensile strength of 24 MPa
which is beyond the tensile strength of any cement paste from hydration.
We unambiguously show the contact bonding between C-S-H solid,
instead of the total porosity, is key to its bulk strength. The presence of
surface water weakens the bonding between C-S-H solid, while C/S has a
non-linear effect on the bonding efficiency. Our results also provide
novel methods to remove the scale effect of C-S-H, which enables the
study of other microscale property of C-S-H using macroscale probes.
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Cement and Concrete Research 159 (2022) 106858
2. Materials and method
2.1. Preparation of C-S-H powders
C-S-H powders were synthesized at an initial bulk C/S of 0.7, 0.9, 1.1
and 1.3 by mixing stoichiometric amounts of silica fume (SiO2 content of
99.09%), calcium oxide (analytically pure) and boiled deionized water,
at a water-to-solid ratio of 20. The mixtures were stored in high density
polyethylene bottles at 80 ◦ C for 2 months and followed by room tem­
perature curing for 2 months. The bottles were shaken twice every week
to avoid high degree of sedimentation and reduce the amount of ag­
gregation. Subsequently, the products were vacuum filtered and washed
with isopropanol using 0.45 μm filter papers in a N2-filled glovebox to
prevent carbonation. The filtered C-S-H were then stored in an oven
(40 ◦ C) for 15 days until the free water in the sample (evaporable at
105 ◦ C) was in the range of 20–30%. The oven was vacuumed to 0.1 MPa
by a pump once every day to accelerate the drying and to avoid
carbonation. As shown later, the achieved C/S was close to or slightly
deviated from the designed value. Thus the C-S-H powders are hereafter
denoted as C/S_0.7, C/S_0.9, C/S_1.1 and C/S_1.3.
Each of the four C-S-H powders were divided into two groups and
transferred to two desiccators with RH of 8% and 100% respectively.
These RHs were achieved using saturated salt solutions placed at the
bottom of the desiccators, i.e. saturated NaOH solution for 8% and
deionized water for 100% [55]. Due to the constant evaporation of
moisture from C-S-H, the measured RH for the 8% RH desiccator may
reach 20% initially. The humidity levels were monitored using an
electronic humidity reader. The free water contents of all samples were
monitored once every few days (Fig. 1a). It was decided that after two
months the free water contents of the samples were equilibrated, at
~25% under 100% RH and ~10% under 8% RH. These two extreme
values of RH were used to investigate the influence of water on the pore
structure formation and strength origination in the subsequent high
pressure mechanical compaction experiments.
2.2. High pressure mechanical compaction of C-S-H powders
To investigate whether and how C-S-H powders gain strength
through microscale bonding, a compacting process was practised as
follows. C-S-H powders were finely ground by hand using agate pestle
and mortar for 15 min. The value of Dv50 is 20 μm, and the particle size
distribution (PSD) was measured by a HORIBA Laser Diffractor based on
Mie theory [56]. The powders were first dispersed in pure water and
then the measurement was carried out for 10 s with constant ultrasonic
treatment. As for the refractive index (m = n − ik), the n of pure water is
1.33 and the n and k of C-S-H are 1.6 and 0.001 respectively. The C-S-H
powders were placed in a steel die of internal diameter Φ10 or Φ20 mm,
and a height of 50 mm (Fig. 1b). The powder was compressed by a
hydraulic press (Samuel Denison 3000 kN Compression Machine) at a
loading rate of ~125 MPa/min. When reaching the designated
maximum load (300, 1000 and 2000 MPa), the pressure was held con­
stant for 3 min followed by a rapid unloading. Dense C-S-H pellets were
then demoulded from the die, and used for subsequent mechanical and
microstructural investigations.
Powder compression has been often used to make C-S-H pellets for
nano-indentation studies [36,50]. Inspired by the author’s previous
high-pressure XRD work [57,58], here we used compression loads up to
2000 MPa, which for the first time allowed the observation of a signif­
icant bonding among C-S-H solid particles.
2.3. Characterization of the synthesized C-S-H powders
Differential thermal analysis (DTA) and thermo gravimetry (TG)
study were conducted on C-S-H powders using a Shimadzu TG Analyzer.
The samples were heated at 20 ◦ C/min from 30 ◦ C to 950 ◦ C under a N2
flow of 100 ml/min. X-ray diffractometer (LabX XRD-6000, Shimadzu
Z. Zhang et al.
Fig. 1. Preparation of compacted C-S-H pellets. (a) Water content evolution under different RH conditions; (b) The process of making compacted C-S-H pellet, and (c)
Monitoring the weight of C-S-H when equilibrating under 8% and 100% RH.
diffractometer) was conducted to identify the major crystalline phases.
The test was performed at 40 kV, 30 mA and over a Cu-Kα 2θ range of 5◦ -
60◦ , at scan rate of 1.5◦ /min. The analysis was performed using a
commercial software HighScore Plus.
The ionic composition of the filtered solutions was measured by
Inductive Coupled Plasma-Optical Emission Spectroscopy (ICP-OES,
Agilent 5110) to supplement the results of TG and XRD analysis [4].
Mass balance calculations were performed to quantify the C/S in the
synthesized C-S-H powders, following the previously reported approach
[59].
The nano-morphology of powders was imaged by TEM (transmission
electronic microscopy, JEM 2010F HRTEM) measurement. This system
was operated at an accelerating voltage of 200 kV. The measurement
was conducted at room temperature with powders spread on a carbon-
coated copper TEM grid. The density of the C-S-H solids was measured
using helium pycnometer (ULTRAPYC 1200e). The samples used in the
density measurement were processed according to BS ISO 12154-2014
[60]. It was vacuum-dried under 105 ◦ C for one day to minimize the
water content in pore spaces down to the interlayer region.
2.4. Pore structure of C-S-H pellets
The total porosity of the compressed C-S-H pellets was measured by
quantifying the interlayer, gel and capillary porosity respectively using
weight loss from different drying conditions and the 1H NMR relaxom­
etry data. The weights of pellets made from all initial powder conditions
were monitored at three conditions: 100% RH, 8% RH and 105 ◦ C.
Multiple weighing was performed until the sample weight was constant,
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Cement and Concrete Research 159 (2022) 106858
i.e. ~14 days for 100% and 8% RH, and 30 min for 105 ◦ C (Fig. 1c).
These three conditions correspond to complete saturation, interlayer-
water dominant with much reduced interparticle water, and nearly
complete dryness with little interlayer water, respectively [61,62]. Thus
the following porosity can be calculated:
minterlayer× ρwater
φinterlayer = (1)
Vtotal
mgel+cap× ρwater
φgel+cap = (2)
Vtotal
where φinterlayer is the interlayer porosity; ρwater is the density of water.
The minterlayer is the quantity of interlayer water, as measured by the
weight loss from 8% RH to 105 ◦ C. The mgel+cap is the mass of water in
gel and capillary pores, and was measured by the weight loss from 100%
to 8% RH. Vtotal is the volume of the pellets at 100% RH; φgel+cap is the
gel and capillary porosity in total. Note that the pellets made from 8%
RH-equilibrated powder were first equilibrated at 8% RH, followed by
100% RH and 105 ◦ C. For all samples, the difference of Vtotal from 100%
to 8% was found to be negligibly small.
After a complete saturation (equilibrated at 100% RH), all pellets
were studied by 1H NMR to further differentiate gel and capillary
porosity. A home-made static magnetic field of 0.7 T was used, at a
resonance frequency of 30.952 MHz and a gradient of 400 mT/m.
Spin–spin relaxation time (T2) values were obtained by a conventional
CPMG pulse sequence, with an echo time of 150 μs, total 2048 echoes,
recording window 100 μs, a repetition time of 10 s, pulse length of 9 μs.
A total 16 measurements were averaged for each sample. The processing
Z. Zhang et al. Cement and Concrete Research 159 (2022) 106858

of the signal followed the method reported in [63]. Table 1

Field emission scanning electron microscope (FE-SEM - Hitachi Sample information for mechanical tests.
Regulus 8230) was used to image the microscale morphology of the Properties Test methods Specimens
pellets, at the back-scattered electron (BSE) mode and an accelerating
Size (mm) Number of
voltage of 20 kV. The samples were from the fragments after the splitting tests
tensile tests. To prepare the SEM-BSE samples, SiC papers of 20 μm and
Splitting tensile BS EN 12390-6-2009 ∅75 × 150a, ∅75 3 (per size)
10 μm were first used to pre-polish the surface of the C-S-H solid, fol­ strength [66] × 30a
lowed by impregnation of a low-viscosity epoxy resin (EpoFix Kit). After ∅50 × 100a,∅50
24 h of hardening, the sample surface was further polished using oil- × 20a
based monocrystalline diamond suspension, with AutoMet Lapping Oil ∅20 × 40a, ∅20
× 8a, b
as lubricant. The polishing was conducted on a Buehler AutoMet
∅10 × 20a, ∅10
polisher with a constantly applied normal load of 15 N. The sample was × 4a
polished for 1 h with 3 μm diamond fluid, followed by 2 h with 1 μm Rockwell hardness ASTM E18 [67] ∅10 × 4 6 (per
diamond fluid. Isopropanol ultrasonic batch was frequently used to sample)
clean the polished surface. Vickers hardness ASTM E384 ∅10 × 4 9 (per
[50,68,69] sample)
a
2.5. Mechanical property tests of the pellets The size of white cement paste for splitting tensile test.
b
The size of C-S-H pellets for splitting tensile test.
Traditional assessment of mechanical properties using standard size
samples was inappropriate as the pellets were not large enough. A series of forming more ordered stacking structure from relatively disordered
of self-consistent evaluating methods were used to explore the me­ stacking, and the stacking order is more readily achieved at lower C/S.
chanical properties of the pellets in different length scales. The splitting In all XRD data, carbonate phases are not identified.
tensile strength, rather than the compression strength, was used to TG data reveal the major weight loss of all powders to be the water
represent the macro strength, as the former always provided an unam­ loss from C-S-H (Fig. 2b). There is no sign of calcium hydroxide in any
biguous fracture. A Denison 15/250 kN Flexure and Compression powders, and very limited amount of carbonate phases only in C/S_1.1
Testing Machine with a displacement control of 0.04 mm/min was used and C/S_1.3. This is confirmed by the DTA result, where the water-loss
for the compacted specimens under compressive loading so that the from C-S-H (below 500 ◦ C) and the wollastonite transformation
whole testing time was around 1–2 min to eliminate the dynamic effect. (~880 ◦ C) are the dominant events in all samples, with trace of CO2-
This approach is also frequently used in testing other materials with non- release in C/S_1.1 and C/S_1.3 (~700 ◦ C).
standard sizes [64,65]. To estimate the size effect, white cement paste The amount of remnant quartz and calcium carbonate were esti­
samples of identical size as the pellets and of size up to the standard mated using Rietveld refinement from the XRD data [71] and weight-
strength (cubes 50 mm on each side) testing size were used as control loss in TG data [72] respectively (see Table 2). Concentration of the
samples. The water-to-cement ratio of the pastes was 0.45. They were aqueous [Ca] and [Si] were measured by ICP-OES. With these data, a
tested after 28-days standard curing, with a compressive strength of 37.7 mass balance calculation (Eq. (3)) was performed to quantify the final
± 2.4 MPa. C/S in the obtained C-S-H powders (Table 2).
Hardness test has an advantage to assess the mechanical properties of /
materials without being influenced by discrete initial defects (voids, Cainput − CaCaCO3 − [Ca]aqueous
C Sfinal = (3)
cracks, etc.), which may significantly influence the bulk strength. Siinput − Siquartz − [Si]aqueous
Although empirical in nature, hardness test can be correlated to intrinsic
tensile strength for materials like alloys. Here, Superficial Rockwell 3.1.2. Nano-morphology and solid density of C-S-H powders
hardness (Zwick Roell® ZHR8150LK mode universal Rockwell hardness The solid density of C-S-H particles (excluding gel and capillary
tester) and Vickers hardness (HMV SHIMADZU) were chosen since the pores) increases with the increase of C/S (Fig. 3a). This observation
result can be compared with reported data on cementitious materials. agrees with previous studies that the C/S increase is accompanied by a
The fact that they test the same property in different length scales makes reduction in the interlayer spacing and an enrichment of Ca and water in
them ideal tools to evaluate the size effect of the mechanical property of the interlayer [31]. The two effects together densify C-S-H solid at
the pellets. This is a common approach in metallic material testing, but higher C/S.
seldom reported for cementitious materials. The particle size distribution is shown in Fig. 3b, with Dv50 ~ 20 μm.
The pellets were imbedded in epoxy for better fixation, and the For more homogeneous compaction the particles were sieved through
measurement was performed on the top-side surface of the pellets. Note 100 μm. The morphology of randomly selected C-S-H particles were
that the epoxy did not impregnate the pore-structure of the pellets. observed using TEM (Fig. 3c-e). The particles were agglomerations of
Table 1 summarizes the sample information for mechanical tests. finer C-S-H units with a foil/sheet-like feature. This nano-morphology
agrees with several reported work [43,73,74]. The TEM images
3. Results (Fig. 3c and e) also reveal abundant pore space between the nano-sheets.
They are at nanometre scale and may host liquid water depending on the
3.1. Characterization of C-S-H powders environmental RH. It will be shown later that the effort of pellet
compaction eliminates most of these pores, while the original quantity
3.1.1. Chemical composition of water in the pores is critical to the degree of compaction and the
The XRD data indicate that C-S-H is the dominant phase in all sam­ mechanical property of the obtained pellets.
ples, except for C/S_0.7 where a notable amount of quartz is observed
(Fig. 2a). At 80 ◦ C curing condition, crystallinity of C-S-H is obviously 3.2. Microstructure of the compacted pellets
better than that of C-S-H cured at room temperature. This is indicated by
the small peak width and the splitting of the major C-S-H peak at 29◦ - 3.2.1. Density and total porosity
31◦ . Only when the ab-plane is more ordered, would this peak-splitting The bulk density of the pellets is shown in Fig. 4a (8% RH) and 4b
be observed [70]. The basal peak is near 6◦ , suggesting a basal spacing (100% RH). Apparently, density increases at higher compressing pres­
near 14 Å. Note that a broad hump overlaps with the sharp basal peak in sure, but is not a clear function of C/S. For the freshly compacted pellets
C/S_0.9 and C/S_1.1, suggesting that the sample might be in the process at the same pressure and C/S, the density seems slightly larger when

4
Z. Zhang et al. Cement and Concrete Research 159 (2022) 106858

Fig. 2. The synthesized C-S-H powders characterized by (a) XRD and (b) TGA.

Table 2
Chemical composition of the synthesized C-S-H powders and the solution.
Powder Starting C/S Residual quartz (%) Residual CaCO3 (%) [Ca] (mmol/L) [Si] (mmol/L) pH Final C/S in C-S-H

C/S_0.7 0.7 13.9 0.35 0.087 0.114 10.85 0.90

C/S_0.9 0.9 3.1 0.38 0.191 0.128 10.90 0.95
C/S_1.1 1.1 0 0.63 0.302 0.009 10.93 1.09
C/S_1.3 1.3 0 1.00 0.320 0.008 11.00 1.29

Fig. 3. Physical properties of C-S-H powders. (a) Solid density of C-S-H particles in this study (blue points) compared with literature data [62] of (1) D-dried C-S-H
(all evaporable water removed), and (2) single calcium silicate layer; (b) Particle size distribution of C-S-H powders after grinding for 15 min. The Dv50 is 20 μm; (c-e)
TEM graphs of C-S-H particles. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

using powders equilibrated at 100% RH than at 8% RH. However, powders were more saturated than that in the 8% RH-equilibrated
further equilibrating the 100% RH pellets in an 8% RH condition led to a powders. After compaction, the pellets of the former powders were
reduction of the bulk density (dashed lined density in Fig. 4(b)). This can 100% saturated, whereas the pellets of the latter were only partially
be explained by the fact that the pores of the 100% RH-equilibrated saturated. Thus, the bulk density of the former is higher due to the mass

5
Z. Zhang et al.
Fig. 4. Density and total porosity of C-S-H pellets made from powders originally equilibrated at (a, c) 8% RH and (b, d) 100% RH.
of the water that fully saturates the pore structure. When the former was
further equilibrated at 8% RH, its pore was partially dried, and thus the
bulk density reduced. During the compaction, we observed the out­
flowing of liquid water from the mould for the 100% RH-equilibrated
powders, but not for the 8% RH-equilibrated powders, which supports
the above interpretation.
The total porosity of pellets was measured using the methods in
Section 2.4, as shown in Fig. 4c and d. For 8% RH-equilibrated powders,
the resulting pellets are less porous when the compaction pressure is
higher, ranging from 0.1–0.2 at 2000 MPa, to 0.2–0.3 at 1000 MPa and
0.4–0.5 at 300 MPa. Interestingly, this tendency barely applies to 100%
RH-equilibrated powders, where the porosity lies between 0.2 and 0.3
for all compaction pressure. This suggests that, with water fully satu­
rating the pores in the powder, compaction is easier than dry powders at
lower pressure, but more difficult at higher pressure. More evidence
from microstructure observation will be provided later to support this
hypothesis. There also seems an increasing trend for porosity as C/S
increases for the 100% RH-equilibrated powders, which is not observed
for the 8% RH-equilibrated powders.
3.2.2. Microstructure observation by SEM
To further investigate the microstructure of the compacted pellets,
samples made from C/S_1.1 powders were imaged by SEM (Fig. 5). Here
we displayed the representative images for initial powder RH of 8% and
100%, compacted by 300 MPa and 2000 MPa. For 8% RH-equilibrated
powders, non-compacted voids (size of a few micron) were observed
within a smoothly compacted matrix (Fig. 5a and b), whereas such de­
fects were not present when the compaction pressure is 2000 MPa
(Fig. 5c and d). For 100% RH-equilibrated powders, defects were rarely
observed for compaction both at 300 MPa (Fig. 5e and f) and 2000 MPa
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Cement and Concrete Research 159 (2022) 106858
(Fig. 5g and h). This agrees closely with the porosity measurement, that
for dry (8% RH) powders the compaction is significantly improved when
the pressure increases, while 300 MPa is sufficient for an efficient
compaction for wet (100% RH) powders.
3.2.3. Porosimetry measured by 1H NMR
The T2 relaxation signal of fully saturated C/S_1.1 pellets made under
different initial RH condition and pressure are shown in Fig. 6a and b (a
complete set of data for all C/S is available in Appendix B). Two to three
peaks are generally observed. According to reported work [75–77], the
T2 peak at position 0.5–4 ms is assigned to small pores which are
intrinsic parts of the smoothly compacted C-S-H matrix. Based on the T2
values, they are equivalent to gel pores in the hydrated cement paste,
whose size are a few nanometres. The rest two peaks of larger T2 are
assigned to larger pores and voids (equivalent to the capillary pores in
hydrated paste). The integrated area of each peak is linearly propor­
tional to the quantity of water in the pore of corresponding size [76],
thus allowing quantifying the ratio of gel porosity to capillary porosity in
the pellets. Using the method in Section 2.4, the differentiation of three
different pore spaces are conducted as shown in Fig. 6c and d.
For all pellets, the capillary porosity is nearly negligible. It is occa­
sionally observed that the capillary porosity increases at higher pres­
sure. We interpret this to be due to the defects caused by demoulding the
pellets at higher pressure, when we had to use large compression load to
push it out of the mould. For pellets made from dry powders, there is a
substantial reduction of gel porosity when pressure increases, while only
a slight reduction of interlayer porosity is generally observed (Fig. 6c).
For pellets made from wet powders, a slight reduction of total porosity is
observed. The correlation between compaction pressure and porosity is
weak. This again agrees with the microstructure and density study, that
Z. Zhang et al. Cement and Concrete Research 159 (2022) 106858

Fig. 5. SEM images of microstructure of the compacted pellets made from (a, b) 8% RH-equilibrated powders at 300 MPa, (c, d) 8% RH-equilibrated powders at
2000 MPa, (e, f) 100% RH-equilibrated powders at 300 MPa, and (g, h) 100% RH-equilibrated powders at 2000 MPa. The initial C/S of all samples here are 1.1. Line
scratches are from sample polishing.

300 MPa is sufficient to compress the powders efficiently when they are
saturated with water. Lastly, the effect of C/S seems not well defined.
100% RH-equilibrated powders were also tested (Fig. 6b) as a contrast
and there was mainly capillary water.
3.3. Mechanical properties of the pellets
3.3.1. Macro and micro hardness
The Superficial Rockwell macro hardness test was performed on the
top-side surface (indentation surface in Fig. 7a) of the pellets, with a
general indent depth < 1 mm. The thickness of pellets is around 4 mm.
The typical indent size and depth of micro-indentation is 10–40 μm
(Fig. 7b).
As shown in Fig. 7c, without differentiating the influence of C/S, the
macro (Superficial Rockwell) hardness of pellets is clearly higher if
made from dry powders. The increase of compacting pressure from 300
MPa to 1000 MPa clearly increases the macro hardness. A further in­
crease from 1000 MPa to 2000 MPa results in only a slight increase of
macro hardness. When plotted as a function of C/S (Fig. 7d), the macro
hardness generally decreases when C/S increases from 0.7 to 1.1, and
slightly increases when C/S further increases to 1.3. The only exception
is for the pellets made from dry powders compressed under 300 MPa.
Recalling the SEM micro-morphology (Fig. 5a and b), the 8% RH_300
MPa samples are the only samples that have clear defects and voids.
Therefore, it is very likely that their macro hardness is dominated more
by these defects, instead of the intrinsic bonding within C-S-H solid.
Micro (Vickers) hardness was tested using a rectangular pyramid
probe (Fig. 7b). As shown in Fig. 7e, the decreasing trend with the in­
crease of C/S up to 1.1 and a slight increase when C/S further increases
to 1.3 is again observed for several sample series. In the 100% RH_1000

7
Z. Zhang et al.
Fig. 6. The T2 signal (a, b) and pore size distribution (c, d) of C-S-H pellets as a function of RH and compacting pressure. T2 signal of only C/S_1.1 is shown here for
simplicity. A complete set of data is available in the Appendix B. In (c) and (d), the three columns of each C/S correspond to compacting pressure (from left to right)
300, 1000, and 2000 MPa.
MPa and 100% RH_2000 MPa series, the micro hardness further de­
creases when C/S increases from 1.1 to 1.3. Again the 8% RH_300 MPa
samples show a different trend than the others, very likely due to the
ubiquitous presence of micro-defects. Overall, both the macro and micro
indentation results suggest: 1) a parabolic behaviour as a function of C/
S, with minimum hardness achieved when C/S is ~1.1; 2) C-S-H pellets
from the compaction of dry powders are substantially more resistant to
indentation than those made from wet powders.
Two sets of reference data are included in Fig. 7e. Ref_1 is a high
density C-S-H in hydrated cement [78], with a micro Vickers hardness
(~90 HV) similar to our pellets compressed at 1000 MPa. The result is
not unexpected as both have porosity near 20% ~ 30% [81]. Ref_2 is
synthesized calcium silicate hydrate compacted under ~335 MPa [79],
thus with a hardness comparable to our pellets compacted at 300 MPa.
The micro and macro hardness of C-S-H pellets were plotted together
with the results of several solid materials [69] (Fig. 8). The data points of
pellets made from dry powers (sphere dots) sit more closely on the trend
line of metallic materials, whereas the pellets made from wet powders
are usually below the results of metallic materials, particularly when the
compacting pressure is low. This may suggest that different mechanisms
are dominating the macroscale failure of C-S-H pellets made from wet
powders and dry powders. For solid matrix with the same micro hard­
ness, a certain mechanism results in an easier failure of pellets made
from wet powders at macroscale, compared with its counterparts from
dry powers and with metallic materials.
8
Cement and Concrete Research 159 (2022) 106858
3.3.2. Splitting tensile strength
The compacted pellets were cylindrical. Thus a splitting tensile test
was performed to assess their macro strength. The setup is similar to a
standard Brazilian splitting test (BS-EN 12390–6 [66]). The strength of
solid usually increases as its size decreases [82]. Since the pellets were
relatively small, we prepared and tested cement paste samples at various
size (Table 1) to assess the size effect, and to compare the strength of the
pellets with hydrated C-S-H matrix in a meaningful way. Splitting tensile
strength was calculated using Eq. (4).
2P
fct = (4)
πdh
where fct is the splitting tensile strength; P is the is the maximum load;
d is the designated cross-sectional dimension; h is the length of the line
of contact (i.e. sample thickness).
For white cement paste samples, two height-to-diameter ratios (H/D
= 2 and 0.4) were chosen and the water cement ratio was 0.45. As shown
in Fig. 9a, a hardened cement paste with standard splitting tensile
strength ~2 MPa, has a tensile strength of 3– 4 MPa when tested at the
same size of the C-S-H pellets. In comparison, the tensile strength of
pellets made from wet powders are in the range of 2–10 MPa, which
seems independent of the C/S and the compacting pressure (Fig. 9b).
Meanwhile, the pellets made from dry powders have a tensile strength of
8–15 MPa when compacted by 300 MPa, and 10–24 MPa when com­
pacted by 1000 MPa. Regarding the influence of C/S, a trend line
opposite to the indentation hardness is observed for dry powder pellets
Z. Zhang et al. Cement and Concrete Research 159 (2022) 106858

Fig. 7. Hardness of C-S-H pellets. (a) Schematic representation of the C-S-H pellets being indented; (b) An example optical image of micro indent; (c) Rockwell
hardness as a function of compacting pressure and initial RH; (d) Rockwell hardness as a function of compacting pressure and C/S; (e) Vickers hardness compared
with reference values. Ref_1: high density C-S-H in hydrated cement [78]; Ref_2: synthesized calcium silicate compacted under ~335 MPa [79,80].

under both pressure values, i.e. the tensile strength at C/S ~ 1.1 is the
highest.
The results of 2000 MPa compacting load is not included here,
because macro-cracks were often generated in the pellets during the
difficult demoulding. The tensile strength was then unreasonably low
due to these cracks. Note that these macro cracks were not likely to
affect the hardness test, as the testing was on the top-surface with a
depth that would not reach the demoulding cracks. Despite that the
splitting strength may be uncontrollably influenced by the demoulding
defects, the following observations can be confirmed.
1) C-S-H pellets made from dry powders exhibit much higher splitting
tensile strength than the counterparts made from wet powders.
2) C-S-H pellets can reach a macro tensile strength of 24 MPa, which is
one order of magnitude larger than the hydrated cement paste. It
suggests that C-S-H as a binding material can exhibit a much higher
macro tensile strength than what the cement and concrete industry
has seen.

9
Z. Zhang et al.
Fig. 8. The correlation between macro and micro hardness data.
Fig. 9. Splitting tensile test: (a) size effect assessed for white cement paste samples. H/D is the height-to-diameter ratio of the samples; (b) splitting tensile strength of
C-S-H pellets.
4. Discussion
4.1. The origin of strength during high pressure mechanical compacting
process
From C-S-H powders with no internal cohesion, compacting under
300–2000 MPa endows strength in the resulted pellets. The measured
tensile strength is one order of magnitude higher than the conventional
hydrated cement paste. There is only one possible explanation to the
origin of strength at nano-scale, i.e. the C-S-H particles achieved cohe­
sion/bonding with each other at the region of close surface contact (red
dash line in Fig. 10a). This phenomenon has been observed for other
minerals such as calcium carbonate [54]. Surface contact bonding re­
sults in an integrated bulk matrix that has tensile strength >10 MPa at a
bulk porosity as high as 42% (i.e. the 8% RH_300 MPa pellets).
The nano-structural change during compacting a wet powder is
distinct from the case of a dry powder. The total porosity of wet powder
compacted pellets remain constantly in the range of 20% to 30%, with a
slight decrease as pressure increases. In contrast, the porosity of dry
powder compacted pellets drops substantially from >40% at 300 MPa to
<20% at 2000 MPa. According to reported works [83,84], mechanical
loading causes redistribution of water in C-S-H pore structure. The
presence of fully saturated liquid water in wet powders creates a hy­
drostatic resistance against the compacting, so that the increase of
pressure did not result in much more removal of non-solid space.
10
Cement and Concrete Research 159 (2022) 106858
Meanwhile for the 8% RH-dried powders the water between particles
was much reduced, resulting in a largely reduced hydraulic pressure.
The compacting of solid then merely depends on the realignment of solid
particles, where the resistance is mainly the friction and repulsion be­
tween solids. This resistance was observed to surrender to a higher
pressure value, e.g. 1000 and 2000 MPa, where the interlayer space
became the dominate non-solid spaces. Strictly speaking, interlayer
space is an intrinsic part of C-S-H layer structure. Here, without
intending to challenge this concept, the interlayer space is compared
with other pore space merely because they all generate 1H NMR T2
signal.
One observation that is worth particular discussion is that, wet
powders seem more easily compacted than dry powders at lower pres­
sure (i.e. 300 MPa). It has been reported that the formation of preferred
orientation is a key process in the compacting of layer C-S-H under
deviatoric stress [57]. The presence of water is shown to greatly facili­
tate this layer-alignment process [58]. This is consistent with the long-
known phenomena that cement paste creeps faster in saturated condi­
tion than in dry condition [85], and also with a recent molecular scale
calculation [86]. When compacting pressure is 2000 MPa, the dry
powder achieved a porosity as low as 12%, with gel and capillary pore
almost all removed. It suggests this pressure is high enough to totally
realign the C-S-H solid even at dry state.
Z. Zhang et al.
Fig. 10. (a) A schematic illustration of the origin of strength in C-S-H pellets; (b) the macro hardness and (c) micro hardness as a function of porosity.
4.2. What dominates the strength of the bulk C-S-H?
4.2.1. Porosity
Dependence of mechanical property of a solid material on its
porosity is universally observed. Here, the micro and macro hardness of
the pellets are plotted as a function of porosity in Fig. 10b and c. The first
thing to notice is that the porosity rule applies more to the pellets made
from dry powders, i.e. their hardness decreases with increased porosity.
Meanwhile, the hardness of wet powder compacted pellets seems to vary
largely within a small range of porosity. This indicates the dominant
factor of strength of the wet powder compacted pellets is not likely the
porosity. Fig. 7c shows that its hardness is higher when the compacting
pressure increases from 300 MPa to 1000 MPa. We interpret this phe­
nomenon as in Fig. 10a, that although the increased pressure did not
significantly reduce porosity, it may push the solid particles closer to
each other and create more closely contacted regions on the surface (red
dash line in Fig. 10a). Behaving like a coarse-grained system, the pellets
have higher hardness values when there are more contacts and bonds
between the solid particles [87]. The same interpretation applies to the
dry powder compaction, whereas in this case the reduction of porosity
and the increase of surface contacting points are both consequences of
higher compacting load. Thus the hardness appears more correlated
with the total porosity.
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Cement and Concrete Research 159 (2022) 106858
4.2.2. Relative humidity
The RH of the original C-S-H powder clearly influences the hardness
(Fig. 7c-e) and tensile strength (Fig. 9b) of the pellets. Dry powder
compaction seems to always result in a stronger pellet than wet powder
compaction, given the same compacting pressure. The biggest contrast is
at 300 MPa compacting, where the wet powder compacted pellets has a
porosity (~25%) only half of that in the dry powder compacted pellets
(~45%), yet the latter has a higher micro & macro hardness and tensile
strength. The only explanation is that surface contacting region in dry
powder compacted pellets has a stronger bond than in the wet powder
compacted pellets. Recent molecular scale studies [88,89] reveal that C-
S-H surface tends to bond tightly with each other only when they are
closer enough (< ~1.5 nm). In the presence of excessive water between
C-S-H surfaces, they are more easily detached or glided under tensile or
shear load, respectively [86,90]. This point can be supported by the
previous research [91] which indicates that salt-free water remains fluid
with a viscosity close to its bulk value even when confined to films down
to only one or two monolayer thick. Thus, the flexible water between
surfaces makes sliding easier which results in weaker resistance to
loading. Our observation is a direct validation of this phenomenon
pictured by molecular simulation.
The above interpretation may also explain the dependence of con­
crete strength on its RH, that dry concrete specimens are always
~10–20% stronger than their wet counterparts. The removal of water
Z. Zhang et al.
between C-S-H solid surface (i.e. the gel pore) in concrete may lead to
the formation of stronger surface bonding, thus a higher strength at
macroscale.
4.2.3. C/S of C-S-H
Influence of C/S to mechanical properties of the pellets is not as
pronounced as RH or compacting pressure. At 2000 MPa compacting
pressure, the resulting porosity in decreasing order is C/S ~ 1.1, 1.3, 0.9,
0.7 for 8% RH powder, and C/S ~ 1.3, 1.1, 0.9, 0.7 for 100% RH
powders (Fig. 4). This order is exactly the same as the increasing order of
micro hardness test, and roughly the order of the macro hardness test. It
may suggest that the influence of C/S takes place via affecting the
compaction efficiency, which unfortunately cannot be further explained
by the data in this work. It was reported that the zeta potential of C-S-H
particles changes from negative to positive with the increase of Ca2+ in
the equilibrated solution [92,93]. Combining the relationship between
C/S of C-S-H and the solution concentration of Ca2+, it seems that the
surface charge of C-S-H may reach the inversion point when C/S is
1.1–1.3 [3]. This suggests that the C-S-H surface configuration and
charge density may result in different repelling/attracting behaviour
during compaction. Future study on C-S-H surface cohesion as a function
of C/S may provide more evidence.
4.3. Size effect of the mechanical property of C-S-H pellets
In this study, correlation between pore structure and mechanical
property is more consistent for micro hardness test, followed by macro
hardness test, and the least consistent in splitting tensile test. Both SEM
images and visual observations after demoulding revealed micro and
macro defects/cracks in the pellets. Therefore, we conclude that the
micro hardness test best reflects the intrinsic mechanical property of the
pellets as the interaction volume is small enough to avoid clear defects in
optical microscope, while the tensile test is too much affected by the
uncontrolled defects. Though we obtained a remarkable tensile strength
of 24 MPa, we believe this value can be substantially lifted for a better
compacted pellets. With improved demoulding technology that avoids
defects, we may eventually eliminate the size effect in the pellets, and
achieve the intrinsic tensile strength of defect-free C-S-H.
Lastly, the compacted pellet is a pure C-S-H matrix with integrated
mechanical property. This practise provides a strategy to synthesize
pure C-S-H volume with controlled pore structure and minimal impu­
rities. This novel approach can be used to design other bulk experiments
that require a pure C-S-H matrix, such as the reactive transport of ions in
C-S-H [94]. So far such samples are vastly missing but urgently needed
in many research topics.
5. Conclusion
This paper reports an approach of manufacturing bulk C-S-H pellets
with strength integrity. The multiscale structure and mechanical
response are investigated as a function of compacting pressure and
initial chemical conditions (i.e. C/S and moisture content). The un­
precedented 2000 MPa compaction results in several novel observa­
tions, which allows the study of the origin of macro-strength in C-S-H
Appendix A
As for hardness test, Rockwell hardness and Vickers hardness were chosen as assessment in macro scale and micro scale respectively. In this study, a
ball indenter with a 1/16-inch (1.6-mm) diameter was adopted with a preliminary test force of 3 kgf (29 N) and a total test force of 15 kgf (147 N) to
obtain a rational range of hardness values for all samples. The Rockwell hardness here precisely is the Rockwell superficial hardness (HR15T). Note
that the depth of an indenter penetrating into the surfaces of samples during the test is generally smaller than 1 mm.
The Vickers hardness number in unit HV (1 HV = 0.01Gpa) is calculated in Eq. (A.1) where P (mN) is the applied force, α is the indenter diagonals
angle equal to 136◦ and D (mm) is the average of diagonals of the indentation.
12
Cement and Concrete Research 159 (2022) 106858
matrix. The following conclusions can be drawn.
1. C-S-H pellets with nearly no capillary porosity is synthesized by
compaction of C-S-H powders with uniaxial compression pressure
above 300 MPa. Porosity of the pellets from dry (8% RH) C-S-H
powders significantly reduces from 40%–50% to 10%–20% when
compression load increases from 300 MPa to 2000 MPa, whereas the
porosity of pellets made from wet C-S-H (100% RH) powders are
constantly within 20% to 30% despite the increase of compacting
load. The presence of excessive water facilitates the particle
compaction at lower pressure (300 MPa) but prevents the compac­
tion at high pressure (2000 MPa).
2. When under the same compaction pressure, the micro and macro
mechanical properties of compacted pellets made from dry powders
(8% RH) are constantly higher than the pellets made from wet
powders (100% RH), regardless of the porosity. Pellets made from
wet powders exhibit a substantial increase in mechanical properties
despite the very slight reduction porosity under increased compact­
ing load. These two discrepancies of property-porosity relationship
suggest that the bonds between closely contacted particles are the
origin of the strength in bulk C-S-H matrix.
3. Under the same compacting pressure, dry C-S-H particles form much
stronger bonding with each other, compared with wet C-S-H
particles.
4. At higher initial RH or higher compacting load, C-S-H with C/S ≥ 1.1
are more difficult to be compacted than C-S-H with lower C/S. The
surface charge density may dominate this behaviour, which needs
further investigation.
5. Macroscale tensile strength of C-S-H matrix reaches >20 MPa,
despite the presence of macro defects. The theoretical tensile
strength of a defect-free C-S-H could be even higher.
CRediT authorship contribution statement
Z. Zhang: Conceptualization, Methodology, Software, Formal anal­
ysis, Investigation, Data Curation, Writing - Original Draft, Visualiza­
tion. Y. Yan: Methodology, Software, Formal analysis. Z. Qu:
Methodology, Software, Formal analysis. G. Geng: Conceptualization,
Methodology, Validation, Resources, Formal analysis, Writing - Review
& Editing, Supervision, Project administration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This research is funded by the MOE Tier 1 project in Singapore under
WBS R-302-000-242-133. The authors would like to thank Dr. Leo Pel
(Eindhoven University of Technology) for his support in 1H NMR
experiment.
Z. Zhang et al. Cement and Concrete Research 159 (2022) 106858

2P sin(α/2)
HV number = × 9.81 × 10− 3
(A.1)
D2
The applied force 980 mN was chosen because many cracks were seen in the specimen with 2000 mN applied force, whereas 500 mN was less
suitable since hardness might be affected by the surface roughness [95]. The load was held for 15 s.
The preparation method of samples is similar to that of samples for SEM observation. The difference is that the resin only fixes the C-S-H pellets
from the surrounding, without any impregnation into the pore structure. The hardness of the pellets is thus not affected by the resin.

Appendix B

Fig. B.1. T2 signal of C-S-H pellets made from 8% RH-equilibrated powders whose C/S is (a) 0.7 (b) 0.9 (c) 1.3. The T2 signal of pellets made from 100% RH-
equilibrated powders and respective powders whose C/S is (d) 0.7, (e) 0.9, and (f) 1.3.

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