Journal of Cleaner Production 220 (2019) 235e252

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Journal of Cleaner Production

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

Characterization on the recycling of waste seashells with Portland

cement towards sustainable cementitious materials
Junjie Wang a, Engui Liu a, *, Liang Li b
a
Engineering Division, New York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, United Arab Emirates
b
Core Technology Platforms, New York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: This work introduces a cleaner production practice of transforming waste seashells into new minerals for
Received 7 October 2018 sustainable cementitious materials. Waste seashells were recycled into fine powder through regular
Received in revised form crushing and ball-milling processes. Multi-scale studies characterized systematically the reaction
24 January 2019
mechanisms of waste seashell powder in ordinary Portland cement system. Seashell powder was studied
Accepted 11 February 2019
Available online 16 February 2019
as both a cement replacement and an additional mineral filler, and its roles were explored through
workability of fresh cement mixtures, hydration of cement, and mechanical behaviors of hardened
cement mixtures. The results indicated that seashell powder enhanced the hydration of cement through
Keywords:
Solid wastes
its physical and chemical interactions with both cement clinker phases and hydration products. The
Seashells mechanical strength of hardened cement mixtures was directly improved when the seashell powder was
Cement used as an additional filler. Additions of seashell powder, either as a cement replacement or an additional
Limestone filler, modified the rheological behaviors of fresh cement mixtures. The hydrated CeSeH matrix phases
Hydration developed with seashell powder were clearly enriched by the embedded well-dispersed nanosized
clusters (with diameter around 5e10 nm). Parallel comparisons between seashell powder and limestone
powder confirmed the higher surface properties and chemical reactivities of seashell powder than
limestone powder in cement system.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction landfilled or directly dumped at the sea areas, which may pose un-
healthy and non-ecological risks. Alternatively, waste shells can be
Recycling solid wastes in cement-based materials has been recycled as a type of renewable biominerals, owing to their
practiced for decades. It reduces remarkably the waste amounts chemical compositions containing >90% calcium carbonate. Cal-
otherwise discharged to the environment through landfilling. It cium carbonate mineral is a major raw material for producing
also promotes sustainable development by utilizing wastes as cement and concrete in the construction sector. Currently, the
cementitious alternatives (Schneider et al., 2011). Usually, by world supply of calcium carbonate is almost entirely from lime-
appropriate proportioning and processing, waste additions to stone mining, which has been considered harmful and unsustain-
cement can enhance both the greenness and performance of able to the natural environment. Thus, recycling waste shells can
cement and concrete, e.g. alkali-activated wastes (Provis et al., supplement nonrenewable limestone mining, as a bio-renewable
2015). Every year, large quantities of waste shells are produced as source of calcium carbonate. Such cleaner production practice, as
by-products in the aquaculture and seafood industries in the world a circular economy, can potentially bring extra profits to the sea-
(Food and Agriculture Organization of the United Nations, 2016). food and aquaculture industries, also provide ecological benefits to
Although it seems difficult to quantify, some more than 10e20 the natural environment.
million tons of waste shells are being discarded yearly from pro- As the geological calcium carbonate, limestone has been long
cessing seashells (Alvarenga et al., 2012; Barros et al., 2009; and widely used as the raw ingredient for cement production, and
Lertwattanaruk et al., 2012), crabs, shrimps, and lobsters (Yan and as the replacement to cement during recent decades to reduce
Chen, 2015) in the world. Those waste shells are normally carbon footprint of cement production (Ingram and Daugherty,
1991; Moon et al., 2017; Ramezanianpour et al., 2009; Vuk et al.,
2001; Ye et al., 2007). The addition of limestone to cement as a
* Corresponding author. replacement has been widely accepted in the field, because it
E-mail address: [email protected] (E. Liu). promotes both the greening and high performance of cement-

https://doi.org/10.1016/j.jclepro.2019.02.122
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
236 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

based materials. However, the addition of waste shells (the bio- mechanical testing, and microstructure exploring on the green
logical calcium carbonate) to cement hasn't attained much research cementitious systems with seashell powder.
attention, especially in the form of grounded powder. The poly-
morphic forms of calcium carbonate in limestone and waste shells 2. Experiment program
have been determined as the calcite and aragonite, respectively. In
general, calcite is a thermodynamically stable form of calcium 2.1. Materials preparation
carbonate; while aragonite is a metastable form which is more
active than calcite in chemistry. 2.1.1. Seashell powder preparation
During past decades, there have been uses of waste seashells in Waste seashells (around 3 kg) from local seafood industry were
cement-based materials, such as the crushed seashell sand (Kuo crushed into 1 cm pieces, followed by transporting into two 2-L
et al., 2013; Safi et al., 2015; Wahyuni et al., 2014; Wang et al., porcelain jars with 40 porcelain balls ranging from
2013; Yoon et al., 2003) or coarse aggregate (Martínez-García 19 mme32 mm in diameter (mixed) in each jar. Crushed waste
et al., 2017; Nguyen et al., 2013) in concrete. Owing to the inferior seashells were then ball-milled in dry condition at jar rotational
surface properties (texture, shape) and low mechanical strength, speed 30 rpm for about 8 h to become fine powder. In Fig. 1, particle
crushed seashells failed to enhance the engineering performances size distributions are reported for seashell powder, limestone
of concrete when used as the aggregates, for example, the consis- powder, and OPC (ordinary Portland cement) powder used in this
tency of fresh concrete mixture, the compactness of hardening study, wherein the average particle size of cement powder, seashell
matrix, and the compressive strength of hardened concrete all powder, and limestone powder is about 30 mm, 60 mm, and 5 mm,
declined. It seems unpractical to recycle waste seashells as the respectively. Among three powders, seashell powder contains 12%
aggregates for concrete, instead, it tends to be more economical and volume of particles smaller than 1 mm (towards the nanoscale
practical to recycle the grounded waste seashells as a powder filler level), while the same for OPC powder and limestone powder is 5%,
or cement replacement in green cement-based materials. This and 7%, respectively. By nitrogen adsorption experiment and BET
practice is similar to the widespread use of limestone powder in the analysis, the BET surface area of the cement powder, seashell
world cement and concrete production. powder, and limestone powder was 1.2156 m2/g, 2.3061 m2/g, and
Some studies reported the use of grounded waste seashells as a 1.4485 m2/g, respectively. Among the three powders, the surface
powder filler or cement replacement (Ballester et al., 2007; area of seashell powder is much larger than that of cement and
Lertwattanaruk et al., 2012; Olivia et al., 2015) in concrete. In those limestone powders.
applications, waste seashell powder was considered as an inert
ingredient and it was chemically non-reactive to the cementitious 2.1.2. Mixture preparation
system. For that, waste seashell was once treated by high heat and Mixtures were prepared using a benchtop bowl mixer (5-L bowl
decomposed into calcium oxide (raw lime) which could rapidly volume), and mixture proportions are listed in Table 1. Three water-
react with water to form hydrated lime (Li et al., 2015) in cemen- binder (w/b) ratios were selected as 0.40, 0.45 and 0.50, in which w/
titious system. This practice however consumed considerable b denoted the mass ratio between water and binder. The binder
amount of energy for heating, and it also required specialized consisted of OPC and seashell powder (as the cement replacement),
process for avoiding re-carbonation. In our study, the waste that is, w/b ¼ w/(Ca þ OPC). The detailed chemical compositions of
seashell powder was utilized directly as a cementitious material, OPC were reported in our previous paper (Wang et al., 2018). The
and its roles on the physical/mechanical performances, hydration measured bulk density of OPC, seashell powder, and limestone
development, and microstructure of cement system was investi- powder used in this study was 1220, 1310, and 1250 kg/m3,
gated in details. So far, there is insufficient research available to respectively. The mass percentage of seashell powder in the binder
conclude roles of grounded waste seashells in cement system either was expressed as 100 Ca/(Ca þ OPC), and the values were deter-
as a cement replacement or a functional filler. Contrasting results mined as 0, 5, 10, 20, and 40. The symbols of w, Ca and OPC were the
have also been found with the addition of waste seashell powder in mass of deionized water, seashell powder, and Portland cement,
cementitious systems. Multi-scale and in-depth investigations respectively. Specifically, we use the symbol Ca to represent
need to be conducted to reach the confident conclusions of recy- seashell powder, the calcium-based mineral addition. The symbol
cling this economically-cheap, widely-available, and biologically- Ca stands for CaCO3, the primary mineral ingredient in seashell
renewable biomass into the construction sector, to transform the powder. In the following paragraphs and figures, we use the simple
environmental burden into economic profits through producing symbol Ca to represent seashell powder, for the convenience of
green cement-based materials. presenting and discussing the experimental results. Testing of the
Aiming at the cleaner recycle of waste seashells and sustainable materials was conducted at curing ages of 1, 3, 7, 14, 28, and 56 days.
production of green and high-performance cement-based mate-
rials, this work investigated roles of grounded waste seashells on 2.1.3. Mixing procedure
hydration mechanisms and microstructural evolutions of Portland Seashell powder was first dispersed in deionized water through
cement system with additions of waste seashell powder as both an one minute pre-mixing at medium speed (around 60 rpm beater
extra filler and a cement replacement. As a cement replacement, rotational speed), followed by adding the cement powder into the
waste seashell powder was blended into Portland cement at seashell powder suspension within ten seconds under the same
various weight percentage between 0 and 40. As an extra filler, mixing condition. Immediately after adding the cement, the mixing
waste seashell powder was externally added into Portland cement was switched to high speed (around 120 rpm beater rotational
at the weight percentage of 20 to the cement; in parallel, limestone speed) and maintained for two minutes till completion.
powder was also externally added into the same Portland cement
with the same weight percentage. The purpose was to investigate 2.2. Testing methods
differences between biological and geological calcium carbonate
minerals in Portland cement, also between the use of waste 2.2.1. Rheology measurement
seashell powder as an extra filler and as a cement replacement. After mixing, 100 mL fresh cement paste was immediately
Systematic materials characterizations have been performed transferred into a rotational rheometer sample cup. The rheometer
through the rheological measurement, hydration monitoring, is a soft solids test rheometer, and uses vane spindle geometry in
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 237

Fig. 1. XRD pattern for seashell powder and limestone powder (top left); Weight loss curve and thermogravimetric peak for seashell powder and limestone powder (top right);
particle size distribution for OPC, seashell powder, and limestone powder (bottom left).

rate-control mode to characterize the viscosity and yield stress of channel high precision isothermal calorimeter designed for
cement paste. To prevent water evaporation during measurement, measuring hydration kinetics of hydraulic cementitious mixtures.
the top of the cement paste was covered by a 1 mm-thick oil layer On preparation, each one of the cement, seashell powder, and
(Schultz and Struble, 1993). The rheological measurement was then deionized water was weighed according to the mixture pro-
conducted under controlled environment (temperature 20  C, portions, respectively, data recorded up to 0.01 g. Total weight of
relative humidity 70%) throughout the entire testing period. Within the binder (cement with or without seashell powder) was
each measurement, the shear rate was applied to the cement paste constantly determined as 25 g, and the deionized water was
from 0.13 s1 to 235 s1 during a 10-min period. The corresponding adjusted accordingly to the specified water-binder ratio. Each
shear stress was recorded against the shear rate per second during weighted material (either binder or water) was then sealed in its
the same period. Each data set (shear rate vs. shear stress) was own measurement cup. Before testing, all sample cups with
fitted to the Bingham rheological model (using Matlab application), weighted binder or water were stored inside the testing chamber of
which then derived the dynamic yield stress and viscosity for the the isothermal calorimeter, for stabilization conditioned constantly
measured cement paste. at 20  C. After stabilization, the binder and the relevant deionized
water was mixed manually for 2 min with a pre-embedded plastic
2.2.2. Hydration heat measurement rod in the measurement cup. The mixed paste was immediately
Hydration heat of cement mixtures was measured in an 8- sealed within the measurement cup and loaded into the specified
test channel for hydration heat monitoring.

Table 1
Mixture proportions.

Mix ID w/b(CaþOPC) Binder(Ca þ OPC) 2.2.3. Compression test

% Ca %OPC After mixing, the fresh cement paste was casted into 1-inch cube
1 0.40 0 100 molds, vibrated for 10 s, and transported into environmental
2 5 95 chamber maintained at temperature 20  C and relative humidity
3 10 90 96% throughout the entire curing period. Samples were de-molded
4 20 80
after the first 24 h. Compression tests were conducted at curing
5 40 60
ages of 1, 3, 7, 14, 28, and 56 days. An electric-powered universal
6 0.45 0 100 material testing system was used to load the 1-inch cube samples.
7 5 95
The load cell capacity of the testing system was 100 kN, and the rate
8 10 90
9 20 80 of loading was made at 0.02 mm/s by the displacement control. The
10 40 60 compressive strength was calculated from the maximum load
11 0.50 0 100 divided by the loading area of the specimen. Each final compressive
12 5 95 strength was an average of three separate testing values. After
13 10 90 compression test, the sampling work was carefully carried out in
14 20 80 the crushed specimen for the following materials characterizations,
15 40 60
e.g. XRD, TGA.
238 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

2.2.4. Nano-indentation 2.2.7. Fourier-transform infrared spectroscopy (FTIR) measurement

Cylindric samples with dimension of 30 mm diameter and The infrared spectrum of diffused reflectance on the powder
30 mm height were casted for modulus measurement with nano- sample was obtained using an FTIR spectrometer. The powder
indentation. Samples were de-molded after the first 24 h. Curing sample was prepared using the same method as reported in PXRD
of the samples was carried out in the environmental chamber with and TGA sections. The measurement range lied between 600 and
temperature 20  C and relative humidity 96% for 28 days till the 4000 cm1.
nano-indentation test. To prepare the sample for nano-indentation,
the outmost 10 mm-thick part was cut off from each of the two 2.2.8. Scanning electron microscope (SEM) observation
ends of the cylindric sample, saving the middle part (10 mm) for the Selected pieces from the crushed cement paste samples were
test. The purpose was to avoid the edge effect from the two ends. coated with gold for 240 s. The coated sample was then observed
After cutting, the remaining middle part was then manually pol- under the secondary electron imaging mode using a field emission
ished on silicon carbide sand papers with fineness sequence of 100, scanning electron microscope. Fig. 2 shows the particle surface
2000 and 4000 (Davydov et al., 2011). Polished samples were morphologies of seashell powder, limestone powder, and cement
cleaned in ultrasonic bath for 30 min followed by drying with powder. There are many microscopically tiny protuberances, ir-
protection of N2 flow at room temperature (22  C) for 3 h. During regularities, and walls on the surface of seashell powder particles,
nano-indentation test, the CeSeH matrix phases were firstly but the surface textures of the other two powders are relatively
selected under optical mode. After that, a group of 64 indents with smooth. This explains why seashell powder has a big surface area
indentation depth of 200 nm were conducted within an area of (compared to limestone powder and cement powder), which also
1 mm2 on each sample. Information acquired from this series of has been found to positively impact the rheological properties,
indents can be statistically representative for the CeSeH matrix hydration development, and mechanical strength of cement paste,
phases (Constantinides and Ulm, 2004). The test method adopted compared to limestone powder.
in this study was originated from the work done by Oliver and Pharr
(1992). 2.2.9. Transmission electron microscope (TEM) observation
Selected cement paste sample was first grounded into powder
form. The powder was immediately dispersed into isopropyl
2.2.5. X-ray diffraction (XRD) measurement alcohol at a mass ratio of 1:100. This suspension was then sonicated
Selected pieces from the crushed cement paste sample were for 30 min in order to achieve a good dispersion of aggregated
grounded manually into fine powder with a laboratory pestle and CeSeH particles, followed by a 30-min self-sedimentation. After
mortar. Powder X-ray diffraction (PXRD) data was collected on the that, one single drop of supernatant was taken from the settled
sample volume about 1 g each time using a PANalytical Empyrean suspension and placed into the sample grid. The sample on the grid
diffractometer. The instrument was operated at a voltage of 45 kV was allowed to dry under vacuum for 20 min, before it was ready
and a current of 40 mA. The PXRD data was collected with the CuKa for the observation.
radiation over an angular range of 2q between 5 and 70 , acquiring
10 scans for each measurement. The XRD pattern of seashell 3. Results and discussion
powder and limestone powder used in this study is shown in Fig. 1.
Seashell powder is mainly composed of aragonite (a calcium car- 3.1. Heat of hydration
bonate crystal), and limestone powder is mainly composed of
calcite (another calcium carbonate crystal), together with little Through isothermal conduction calorimetric measurement,
amounts of SiO2 and Ca(OH)2, which are indicated in the XRD Figs. 3 and 4 plot the hydration heat flow rate and total heat of
spectrum and thermogravimetric curves in Fig. 1. Calcite is the most hydration for the blended cement mixtures. Within the blended
stable polymorphic form of calcium carbonate, while aragonite is cement mixtures, the cement was replaced by seashell powder at a
the metastable one. mass ratio of 0e40%. The hydration heat flow rate and total heat of
hydration were processed into two scenarios for each blended
cement mixture. Scenario one processed the hydration heat flow
2.2.6. Thermo-gravimetric analysis (TGA) rate and total heat of hydration based on the total weight of
TGA was carried out on the powder sample prepared using the blended binder (seashell powder þ OPC), with the results shown in
same method as used above in the PXRD section. A simultaneous Figs. 3 (b) and Fig. 4 (b). Scenario two however, processed the hy-
thermal analyzer instrument was used to conduct this work and it dration heat flow rate and total heat of hydration based on the
heated the sample under the protection of nitrogen. For each weight of OPC only (OPC), with the results shown in Figs. 3 (a) and
analysis, about 10 mg sample was loaded into the furnace, and Fig. 4 (a). In scenario one, the hydration heat flow rate and total
heated from ambient temperature up to 1100  C at the rate of 10  C/ heat of hydration both decreased with the increase of cement
min. Before the sample was heated, the furnace was first warmed replaced by seashell powder in the blended cement mixtures. This
up and stabilized for 30 min to reach the isothermal condition at was due to the “dilution effect” of seashell powder, which increased
25  C with the ambient atmosphere. In Fig. 1, the weight loss curves the effective water-cement ratio of the blended cement mixtures.
and derivative thermogravimetric peaks are shown for seashell The increased effective water-cement ratio generally reduced the
powder and limestone powder used in this work. Seashell powder rate of hydration reactions. However, seashell powder clearly
decomposed around temperature from 580  C to 780  C centered at accelerated the hydration of C3S (tricalcium silicate, one major
740  C, and lost about 42% of its weight at this range. This weight clinker phase in cement), and it was shown through the early-shift
loss was equivalent to 95.5% CaCO3 in seashell powder, according to of the 10-h hydration heat flow peak in Fig. 3 (b). This peak
the theoretical value of 44% weight loss in pure CaCO3. The appeared earlier by about 20 min to 2 h for the blended cement
decomposition of limestone powder occurred between 600  C and mixtures with varying contents of seashell powder, than the one for
800  C centered at 770  C, and brought about 38% weight loss. This 100%OPC mixture. Seashell powder also promoted the renewed
weight loss was equivalent to 86.4% CaCO3 in the limestone pow- formation of ettringite (and/or the comparable phase). This was
der, which indicated that limestone powder contains some impu- shown by the visibly enhanced shoulder on the 15-h hydration heat
rities (already identified in Fig. 1). flow peak (Bullard et al., 2011) in Fig. 3 (b).
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 239

Fig. 2. Particle surface morphology of: limestone powder (top left), Portland cement powder (top right), and seashell powder (bottom left).

Fig. 3 (c) shows the hydration heat flow rate for the blended of blended cement particles, and the early hydration reactions. The
cement mixtures within the first hour, which was processed based major hydration product at this stage was ettringite. The 100%OPC
on the total weight of the binder. The hydration heat flow within mixture developed the highest hydration heat flow rate. Both 5%Ca
the first hour was contributed by the initial wetting and dissolution and 10%Ca mixtures developed the comparable hydration heat flow

Fig. 3. Hydration heat flow rate of blended cement mixtures: (a) processed based on OPC only; (b) processed based on total binder (Ca þ OPC); (c) processed based on total binder
(Ca þ OPC) within the first hour.
240 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

Fig. 4. Total heat of hydration of blended cement mixtures: (a) processed based on OPC only; (b) processed based on total binder (Ca þ OPC).

rate to the 100%OPC mixture, regardless of the cement content middle-stage cement hydration, in which major silicate clinker
reductions in 5%Ca and 10%Ca mixtures. Right after the first hy- phases begun to hydrate, i.e. C3S, C2S (tricalcium silicate, dicalcium
dration heat flow peak, both 5%Ca and 10%Ca mixtures, and then silicate).
the 20%Ca mixture were found to develop higher heat flow rate Based on the observed hydration heat development, seashell
than the 100%OPC mixture. The 40%Ca mixture also increased its powder was unlikely to be inert. Instead, it enhanced the hydration
hydration heat flow rate during the same time period, although it of cement, which was believably owing to the combined chemical
didn't exceed the 100%OPC mixture as the 5%Ca, 10%Ca, and 20%Ca and physical roles of seashell powder in blended cement mixtures.
mixtures did. All mixtures reached the dormant stage at the end of Physical roles may be achieved by the modified dispersion
the first hour. Through the observation of hydration heat flow (Lertwattanaruk et al., 2012) of cement particles in the hydrating
behavior within the first hour, the formation of calcium carboalu- medium, and the dilution effect of increasing exposure of cement
minate phase can be initiated during this time period. The forma- grains to water. The irregularity and complexity on particle surface
tion of this phase was derived from the reaction between C3A of seashell powder (Fig. 2) can potentially explain its physical roles.
(tricalcium aluminate, one clinker phase in cement) and seashell This surface morphology can promote interactions between
powder. seashell powder and cement particles, also hydration products. It
In scenario two, results shown in Figs. 3 (a) and 4 (a), seashell acted as the plasticizer for cement particles and the nucleating/
powder in the blended cement mixtures was assumed to be inert. seeding sites for hydration products. Chemical roles can be ach-
The hydration heat flow rate and total heat of hydration of the ieved through the dissolution of seashell powder in the high
blended cement mixtures were accordingly processed based on the alkaline cement environment, and the hydration of aluminate and
cement only (OPC). Both the hydration heat flow rate and total heat silicate clinker phases (i.e. C3A, C3S) with the dissociated Ca2þ and
of hydration were found to increase remarkably with the increase CO23 from seashell powder.
of seashell powder, regardless of the increased effective water-
cement ratio when the cement was increasingly replaced by 3.2. Thermogravimetric analysis (TGA)
seashell powder in the blended cement mixtures. The increase in
effective water-cement ratio could reduce the ionic concentrations Fig. 5 shows the TGA results for blended cement mixtures (w/
in the hydrating medium, and thus reduced the hydration heat b ¼ 0.4) at 1 day and 56 days. There are three main temperature
release, but this phenomenon didn't occur. The reason can be owing ranges in the weight loss curves, namely 80e150  C, 380e420  C,
to the extra physical and chemical effects of seashell powder in and 680e740  C. Fig. 6 displays the differential thermogravimetric
cement hydration. The dormant period was evidently shortened in (DTG) curves for blended cement mixtures of 100%OPC and 20%Ca
blended cement mixtures with seashell powder. It was shown in at curing ages of 1 day and 56 days. The three temperature ranges in
Fig. 3 (a) by the earlier-appeared 10-h hydration peak for all the weight loss curve have been connected to the relevant thermal
blended cement mixtures with seashell powder than the same decomposition peaks of the specific phases. Peak 80e150  C in-
peak for 100%OPC mixture. The 10-h peak corresponded to the dicates the water loss from the following phases: ettringite, AFm

Fig. 5. Thermogravimetric weight loss of blended cement mixtures (w/b 0.4) at 1 day and 56 days.
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 241

Fig. 7. Amount of remaining CaCO3 in the mixtures (w/b 0.4) at various curing ages,
Fig. 6. Differential thermogravimetric curves for the mixtures of 100%OPC and 20%Ca quantitatively determined based on the decomposed calcium carbonate.
(w/b 0.4) at 1 day and 56 days.

thermogravimetric peak 380e420  C, representing the weight loss

(calcium carboaluminate and/or monosulfate phase), and the due to the dehydroxylation of portlandite in the hydrated mixtures.
CeSeH. Peak 380e420  C appears due to the decomposition of Similarly, the amount of Ca(OH)2 in the hydrated mixtures was
portlandite [Ca(OH)2]. The presence of peak 680e740  C is attrib- processed into two scenarios: Fig. 8(a) presented weight percent-
uted to the decomposition of calcium carbonate. age of Ca(OH)2 in terms of the total binder (seashell powder þ OPC),
In Fig. 5, the difference in weight loss between blended cement and Fig. 8(b) displayed weight percentage of Ca(OH)2 in terms of
mixtures with seashell powder and 100%OPC mixture decreased the OPC only (OPC). The purpose of showing two scenarios was to
with the curing from 1 day to 56 days. This may indicate a good verify the effect of seashell powder on cement hydration, from the
long-term hydration potentials in the blended cement mixtures perspective of the formation of Ca(OH)2. In general, the amount of
with seashell powder. Ca(OH)2 decreased with the increase of seashell powder in the
Again for peak 80e150  C in Fig. 6, the primary phases associ- blended cement mixtures for each curing age, shown in Fig. 8 (a).
ated with this peak were ettringite and CeSeH (80e100  C) for However, with the continuous curing from 1 day to 56 days, the
100%OPC mixture. While for blended cement mixture with seashell amount of Ca(OH)2 produced in the blended cement mixtures
powder (20%Ca), calcium carboaluminate (AFm) was also clearly gradually increased and approached that produced in 100%OPC
present (100e120  C) from the beginning of 1 day. The 100%OPC mixture. Especially for 5%Ca (Mix ID #2), 10%Ca (Mix ID #3), and
mixture demonstrated a tiny peak of AFm (monosulfate) at 56 days, even 20%Ca (Mix ID #4), the amount of Ca(OH)2 in each one of
and this was owing to the conversion of ettringite (AFt) during the those blended cement mixtures became highly comparable to that
hydration. It was different from the calcium carboaluminate-based in 100%OPC mixture (Mix ID #1) through the curing till 56 days.
AFm phase, which was produced from the participation of seashell Again, if seashell powder was assumed to be an inert addition, it
powder in the cement hydration. In 20%Ca mixture in Fig. 6, the would not have clear effect on the Ca(OH)2 formation. The per-
calcium carboaluminate appeared to be the primary phase at 1 day; centage of Ca(OH)2/OPC processed in the second scenario assumed
in the meantime, both ettringite and CeSeH seemed to be the that the Ca(OH)2 formation was related to OPC only, and had
secondary phases with their peak intensities much lower. From 1 nothing related to seashell powder. The results are shown in Fig. 8
day to 56 days, peak intensities for both ettringite and CeSeH (b). It clearly shows that the amount of Ca(OH)2 increases with the
increased remarkably with the hydration, meanwhile, the peak of increase of seashell powder in the blended cement mixtures, and
calcium carboaluminate phase was always clearly present. also with the continuous curing from 1 day to 56 days.
As mentioned above, peak 580e780  C in Fig. 6 was due to the These phenomena indicate that seashell powder couldn't be
release of CO2 as a result of CaCO3 decomposition. Sources for inert in the blended cement. It participates in, and demonstrates its
CaCO3 in the blended cement mixtures can be the added seashell physical and chemical roles on cement hydration. The formation of
powder, or the carbonated portlandite in the hydrated cement calcium carboaluminate is due to the reaction of dissociated cal-
matrix. Based on the weight loss of CO2, the balance of CaCO3 in cium and carbonate from seashell powder and the aluminate phase
each mixture was calculated, with the results shown in Fig. 7. The from the cement. The main period for the formation of calcium
content of CaCO3 in 100%OPC mixture (Mix ID #1) was relatively carboaluminate has been inferred to be during the early hydration
constant and stabilized during the whole curing period from 1 day within 3 days. The enhanced formation of portlandite has been
to 56 days. This part of CaCO3 was produced by the natural perhaps attributed to the physical role of seashell powder. In
carbonation during mixing, placing, and curing of the mixture. In blended cement mixture, it can be used as a cement dispersant, so
blended cement mixtures with seashell powder, however, the that cement grains can be better dispersed and dissolved; in the
CaCO3 content generally decreased with the curing time. The rate of meantime, it can act as a suspended calcium-based nucleation site,
decrease was higher during early curing age within 3 days, and then which would promote the precipitation of hydration products.
gradually reduced during later curing age beyond 3 days. This in-
dicates that seashell powder was consumed during cement hy-
dration, and the rate of consumption was relatively high at the early 3.3. X-ray diffraction (XRD)
stage of hydration.
Fig. 8 shows the calculated content of Ca(OH)2 in the hydrated XRD patterns of blended cement mixture samples were
blended cement mixtures. The calculation was based on the collected at curing ages of 1, 3, 7, 14, 28, and 56 days. Fig. 9 shows
242 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

Fig. 8. Amount of Ca(OH)2 in the blended cement mixtures (w/b 0.4) at various curing ages, quantitatively determined based on the decomposed portlandite, expressed by: (a)
weight % over the total binder, (b) weight % over the OPC only.

selectively the XRD patterns of samples at 1 day and 56 days, reductions were not as big as those in mixtures of 20%Ca and 40%
representing early-age and later-age hydration, respectively. The Ca, fractions of C2S and C3S were higher than those in 100%OPC
XRD pattern presents various components, including both the mixture. This was believably owing to the higher effective water-
anhydrous and hydrated phases, e.g. C2S, C3S, and ettringite, cal-
cium carboaluminate. In all blended cement mixtures with seashell
powder, calcium carboaluminate was detected, and appeared since
the early hydration at 1 day.
In each XRD pattern, the intensity of the characteristic peak for
either an anhydrous or a hydrated phase can relatively indicate the
quantitative fraction of the phase in the hydrated blended cement
matrix (Klemm and Adams, 1990). Based on that, specific peaks
were determined to represent the corresponding phases relevant to
the roles of seashell powder. In the determination process, the
position of the peak only associated with this phase, and didn't
overlap with any other phases. The intensity of the determined
peak was relatively the highest one among the characteristic peaks
for that phase. In this way, the quantitative (relatively) fractions of
relevant phases in the hydrated blended cement matrix have been
processed for each curing age, with the results shown in Fig. 10.
Major phases including anhydrous phases of C2S and C3S, hydrated
products of ettringite, portlandite, and calcium carboaluminate,
and aragonite (seashell powder) have been followed in the hy-
drated blended cement matrix. Aragonite was present in all the
hydrated blended cement matrix with seashell powder, and its
intensity gradually decreased with the hydration time. The in-
tensity of ettringite increased steadily with the curing age in
blended cement mixtures with seashell powder, but it demon-
strated a decreasing trend in the 100%OPC mixture during 3 dayse7
days. Seashell powder seemed to be able to stabilize and promote
the formation of ettringite in the blended cement mixtures,
compared to that in 100%OPC mixture. (Ramachandran and Chun-
Mei, 1986). It was mainly shown by the gradual increase of ettrin-
gite in the blended cement mixtures with the curing time and the
increase of cement replaced by seashell powder. Calcium carboa-
luminate was detected and appeared since the early hydration of 1
day in all blended cement mixtures with seashell powder. Its in-
tensity increased steadily with the curing time, and the rate of in-
crease escalated with the increase of cement replaced by seashell
powder (shown by the slope of the curve).
The fractions for anhydrous phases of C2S and C3S in blended
cement mixtures varied with both the amount of cement replaced
by seashell powder and the hydration kinetics, compared to those
in 100%OPC mixture. In blended cement mixtures with high
amount of cement replaced by seashell powder (20%Ca and 40%Ca),
fractions of C2S and C3S were smaller than those in 100%OPC
mixture. This was mainly owing to the big reductions in cement Fig. 9. XRD patterns for phases in hydrated blended cement mixtures with varying
content. However, in mixtures of 5%Ca and 10%Ca where cement amounts of cement replaced by seashell powder at curing ages of 1 day and 56 days.
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 243

Fig. 10. Relative weight fractions of C2S and C3S, portlandite, ettringite, aragonite, and calcium carboaluminate in hydrated blended cement mixtures with curing ages.

cement ratios that decreased the rate of hydration. Portlandite was mixture with 40% cement replaced by seashell powder, and in-
the hydration product of both C2S and C3S phases. Seashell powder vestigates the development of hydration products with curing time
seemed to promote the hydration of C2S and C3S phases in blended from 3 days to 56 days. In both figures, relevant compounds and
cement mixtures. The fraction of portlandite in 5%Ca mixture was hydration products have been identified against their characteristic
found comparable to that in 100%OPC mixture, regardless of the peaks in the spectra (Gallucci et al., 2010; García Lodeiro et al.,
cement content reduction and the increase in effective water- 2009; Lecomte et al., 2006). The peak at 3638 cm1 is assigned to
cement ratio. The mixtures with higher amounts of cement portlandite Ca(OH)2 (García Lodeiro et al., 2009; Lecomte et al.,
replaced by seashell powder (10%Ca, 20%Ca, and 40%Ca) all devel- 2006), and the band centered around 1107 cm1 belongs to the
oped reasonably lower fractions of portlandite than that in 100% stretching mode of SeO in ettringite (Ylme
n et al., 2009). Both
OPC mixture due to the big reductions in cement content. peaks at 3407 cm1 and 1641 cm1 are attributed to the OeH bond
of water from hydration products (García Lodeiro et al., 2009;
3.4. Fourier-transform infrared spectroscopy (FTIR) Lecomte et al., 2006). The main peaks at 1475 cm1 and 874 cm1
are assigned to the stretching mode and in-plane bending mode of
Figs. 11 and 12 together present the infrared spectra of hydrated CeO in CaCO3 (García Lodeiro et al., 2009; Lecomte et al., 2006). The
blended cement mixtures. Fig. 11 shows information for each one of peak around 964 cm1 is associated with the main hydration
the blended cement mixtures hydrated for 28 days, including all product of CeSeH (García Lodeiro et al., 2009).
blended cement mixtures with cement replaced by seashell pow- In Fig. 11, the peak intensity for ettringite slightly increases with
der from 0 to 40%. Fig. 12 focuses on one single blended cement the increase of seashell powder in blended cement mixtures,
244 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

CeSeH matrix phases developed in the blended cement mixtures

may therefore appear less strong in the modulus, but the combined
water can be highly useful for continuous hydration and the cor-
responding microstructural development. The dissociated calcium
from seashell powder in the high alkaline and concentrated ionic
cement environment may also contribute to the formation of
CeSeH matrix phases, e.g. with higher Ca/Si ratios (García Lodeiro
et al., 2009). In Fig. 12, it is found that the peak intensity for CeSeH
matrix phases increases with the hydration time, in the meantime,
signal for the combined water decreases, which may point to the
maturing process of the CeSeH matrix phases with hydration time.
The peak intensity for CaCO3 slightly decreases with the hydration
time, shown by the gradual disappearing of the small shoulder in
the characteristic peak versus time. The decrease in the intensity of
CaCO3 peak further brings up the chemical interactions between
seashell powder and the hydrating cement system, e.g. dissociated
calcium and carbonate combined with the aluminate phase to form
calcium carboaluminate (Ingram and Daugherty, 1991).
Fig. 11. Infrared spectra for each one of the blended cement mixtures hydrated for 28
days.
3.5. Rheology

Few studies was reported about the influences of waste seashell

powder on the rheology and workability of cement-based mate-
rials. In this work, Fig. 13 demonstrates the rheological properties
(viscosity and dynamic yield stress) for blended cement mixtures
with seashell powder. As described in the experimental part, the
viscosity and dynamic yield stress were obtained by fitting the
rheological measurement data of shear stress vs. shear rate to the
Bingham model (Felekog lu et al., 2006; Seraj et al., 2016). Both
viscosity and dynamic yield stress decreased with the increase of
seashell powder in blended cement mixtures in Fig. 13. The vis-
cosity for the blended cement mixtures of 5%Ca, 10%Ca, and 20%Ca
was about 87e93%, 75e85%, and 60e79% of the viscosity for the
100%OPC mixture, respectively, with each of the percentage ranges
corresponding to the water-binder ratios of 0.40, 0.45, and 0.50. For
the mixture of 40%Ca, its viscosity was only about 50% of that for
the 100%OPC mixture. The trend of dynamic yield stress appeared
the same as that of viscosity for the blended cement mixtures. The
Fig. 12. Infrared spectra for the blended cement mixture of 40%Ca at various curing rheological characterizations of viscosity and dynamic yield stress
ages from 3 days to 56 days. indicated that addition of seashell powder can extend the flow or
workability of the blended cement mixtures. The modifications can
be partially owing to the dispersion effect of seashell powder in the
indicating again the role of seashell powder in stabilizing the for- blended cement mixtures. As a result, aggregation of cement par-
mation of ettringite. Intensities for both peaks of CeSeH and the ticles was clearly alleviated with the addition of seashell powder. In
combined water were found to increase with the increase of the meantime, the replacement of cement by seashell powder also
seashell powder in blended cement mixtures. This suggests that increased the effective w/c ratio of the blended cement mixtures.
seashell powder may contribute to the development of CeSeH The increase in effective w/c ratio reduced simultaneously the
matrix phases which contains high amount of combined water. The viscosity and dynamic yield stress in the blended cement mixtures.

Fig. 13. Viscosity and dynamic yield stress for the blended cement mixtures with seashell powder.
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 245

Therefore, the addition of waste seashell powder to blended In order to reveal the effect of seashell powder on the strength
cement mixtures (consume less cement) can directly reduce water development, the 1-day compressive strength of blended cement
demand in the fresh mixtures (achieve better performance in the mixtures was taken as the benchmark. Based on that, the per-
hardened mixtures), while maintain sufficient flow and centage increase in compressive strength for all blended cement
workability. mixtures beyond 1 day was processed as a function of cement
replacement by seashell powder, with the result shown in Fig. 15.
The percentage increase in compressive strength was all higher in
3.6. Macro- and micro-mechanical performance blended cement mixtures with seashell powder than that in 100%
OPC mixture. The higher amount of cement replacement by
The mechanical performance of hardened blended cement seashell powder, the higher rate of percentage increase in
mixtures has been characterized by the macroscopic compression compressive strength of the blended cement mixtures. At 56 days,
on the bulk solids (compressive strength), and the microscopic the compressive strength of 100%OPC mixture increased by
nanoindentation on the localized hydrated CeSeH matrix phases 156e207% to those at 1 day. However, the same increase was
(nanoindentation modulus). Figs. 14 and 15 together present the 353e473% for the 40%Ca mixture (40% cement replacement by
development of compressive strength of blended cement mixtures seashell powder). It therefore indicated that seashell powder ad-
with hydration time and the amount of cement replaced by seashell ditions in blended cement demonstrated high potentials in
powder. The compressive strength (Fig. 14) generally decreases improving the compressive strength. This also agreed with the
with the increase of seashell powder in blended cement mixtures, enhanced hydration by seashell powder in the blended cement
and it is closely related to the increase in effective w/c ratio owing mixtures, characterized by e.g. hydration heat, XRD, and TGA in the
to the replacement of cement by seashell powder. The potential preceding sections. These results were also similar to the roles of
effect of seashell powder on strength development in blended limestone powder (geological calcium carbonate) in blended
cement mixtures has been masked by the increase in effective w/c cement mixtures that hydration of cement can be promoted by the
ratio which generally has a stronger effect on compressive strength additions of limestone powder (Kakali et al., 2000; Pe
ra et al., 1999).
of cement-based materials. Fig. 16 shows the indentation modulus of blended cement
mixtures (0.4 w/b ratio) at curing ages of 7 day, 14 day, and 28 days.
The development of indentation modulus at nano-scale level ap-
pears to be consistent with the development of compressive
strength at macro-scale level. The modulus of CeSeH matrix
phases generally decrease with the increase of seashell powder in
blended cement mixtures. There are notable scatters in the
indentation modulus, shown by the error bars in the figure. The
scatters increase with the increase of seashell powder in the
blended cement mixtures. The increased scatters can be owing to
the addition of seashell powder and the increased effective w/c
ratio, which have increased the microstructural and compositional
complexities in the CeSeH matrix phases. The CeSeH matrix
phases can become more complex in the blended cement mixtures
with seashell powder, compared to that in 100%OPC mixture. One
of the complexities is represented by the higher amount of water
incorporated (Constantinides et al., 2003; Constantinides and Ulm,
2004; Davydov et al., 2011) into the hydrated CeSeH matrix pha-
ses, and it has been also observed through FTIR analysis. Another
complexity stems from the enhanced crystallinity and the richness
Fig. 14. Compressive strength of blended cement mixtures as a function of w/b ratio,
cement replacement by seashell powder, and hydration time.

Fig. 15. Percentage increase in compressive strength of blended cement mixtures Fig. 16. Indentation modulus of CeSeH matrix phases in blended cement mixtures
beyond 1 day, based on the 1-day strength. with hydration time of 7, 14, and 28 days (0.4 w/b ratio).
246 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

of hydration products in the CeSeH matrix phases developed in the

blended cement mixtures with seashell powder, which can also be
supported by the XRD analysis. Seashell powder itself is a type of
bio-based calcium carbonate crystals (aragonite, meta-stable), and
it participates at the hydration reactions of blended cement. For
example, it undergoes partial dissolution and precipitation with
cement hydration, which seems to stabilize the formation of
ettringite, promote the growth of calcium carboaluminate, and
facilitate the formation of CeSeH matrix phases including por-
tlandite. Those constituent phases together with their microstruc-
tures at micro- and nano-scale levels have contributed to the
formation of enriched and complexed CeSeH matrix phases in the
blended cement mixtures.
The deviations in indentation modulus partially proves the di-
versity and richness of the indentation modulus values, corre-
sponding to the enriched microstructure and composition in
CeSeH matrix phases. In blended cement mixtures of 5%Ca, 10%Ca,
and 20%Ca, the rate of increase in indentation modulus (based on
the 7-day modulus) with hydration time becomes comparable to
that in 100%OPC mixture, indicating the constructive roles of
seashell powder on modulus development in CeSeH matrix phases
during hydration.
The decrease in macro- and micro-mechanical properties of
hydrated cement mixtures is mainly due to the increase in effective
w/c ratio (it can increase the capillary porosity) when cement is
replaced by seashell powder, but seashell powder clearly exerts
positive influences on the hydration process, hydration products,
and microstructure development in the blended cement system
which can be further engineered to enhance mechanical
performances.

3.7. Microstructural morphology

Fig. 17 shows the surface morphologies of hydrated cement Fig. 17. SEM images showing morphologies of hydrated cement matrix developed in
blended cement mixtures with seashell powder (w/b ratio ¼ 0.4, hydration time 28
matrix developed in blended cement mixtures hydrated for 28 days
days).
(w/b ratio ¼ 0.4). Fig. 18 confirms the formation of calcium car-
boaluminate in hydrated cement matrix with seashell powder. The
calcium carboaluminate generally appears similar to ettringite in has been observed due to the increase in the capillary porosity as a
morphologies, but the elemental compositions of the two phases result of the increase in effective w/c ratio. Therefore, during real
are essentially different. There is no carbon element in ettringite, productions, the water-cement ratio (water content) for blended
but there is carbon in calcium carboaluminate owing to the infused cement mixtures needs to be appropriately reduced, when waste
carbonate dissociated from seashell powder during cement hy- seashell powder is used to replace cement.
dration. Both calcium carboaluminate and ettringite phases have
been observed in the hydrated cement matrix with seashell pow-
der. This agrees with the previous research, reporting that ettringite 3.8. Comparisons between seashell powder and limestone powder
and calcium carboaluminate phases can coexist in the hydrated
cement system with addition of CaCO3 mineral (Ramachandran and This section compares roles of geological and biological calcium
Chun-Mei, 1986). carbonate minerals in ordinary Portland cement (OPC) system. As
In Fig. 17, hydration products developed in 100%OPC mixture mentioned above, seashell powder represents biological calcium
consist typically of the CeSeH, Ca(OH)2, and some amount of carbonate (bio-CaCO3), and limestone powder represents geolog-
ettringite. However, in blended cement mixtures with seashell ical calcium carbonate (geo-CaCO3). In the previous discussion, we
powder (e.g. 20%Ca, 40%Ca), more amounts of ettringite- and cal- noticed the adverse effect of the increased effective w/c ratio on the
cium carboaluminate-like phases can be clearly seen, and tend to mechanical performance of blended cement mixtures with seashell
increase with the increase of seashell powder in the mixtures. It is powder, especially when the effective w/c ratio was largely
found that some ettringite, and especially the calcium carboalu- increased due to big amounts of cement replaced by seashell
minate are formed close to or on the location of seashell powder, powder, e.g. in 40%Ca mixture. Because excess amount of water
which may explain partially why seashell powder enriches the (high w/c ratio) can play a huge impact on the hydration and per-
hydrated cement matrix (forms composited matrix), and promotes formance of cement system, the beneficial effects of seashell
(serves as nucleation sites) the precipitation of hydration products, powder in blended cement mixtures, as a result, can be obscured by
especially the ettringite and calcium carboaluminate the influence of largely increased effective w/c ratio. In order to
(Lertwattanaruk et al., 2012). This is the benefit of having seashell remove the strong influence of the increased effective w/c ratio, and
powder in blended cement, which contributes to a new hydrated visualize clearly the influences of the two calcium carbonate min-
cement matrix with enhanced integrity and cohesiveness. When erals on the hydration and development of OPC system, we fixed
large amount of cement is replaced by seashell powder (e.g. 40%Ca the w/c ratio of the cement paste as 0.40 in this part. Each of the two
mixture) in blended cement, a less dense hydrated cement matrix calcium carbonate minerals (geo-CaCO3 and bio-CaCO3) was then
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 247

Fig. 18. SEM images and elemental analysis on: (a) calcium carboaluminate and ettringite developed in hydrated blended cement mixtures with seashell powder, and (b) ettringite
developed in 100%OPC mixture.

introduced into the cement paste as the additional additive, reactive than limestone powder, which is shown by the higher
respectively, at the same dosage of 20% by mass of cement. The hydration heat flow rate and total heat of hydration achieved in the
materials characterizations were followed by hydration heat composite cement paste with seashell powder than limestone
monitoring, rheological measurement, compressive strength, FTIR powder during the 72 h hydration. In the first hour hydration
analysis, and the TGA, with the results shown in Figs. 19e23. shown in Fig. 19-b, the heat development is mainly caused by the
Clear differences have been found between the two calcium hydration of the C3A phase. Both the seashell powder and lime-
carbonate minerals in the same cement paste. The difference be- stone powder can participate in the hydration of this phase to form
tween calcite (geo-CaCO3) and aragonite (bio-CaCO3) in cement calcium carboaluminate (Ingram and Daugherty, 1991; Moon et al.,
system has been mentioned previously in the literature (Ingram 2017), but the effect of the seashell powder is greater than that of
and Daugherty, 1991), however, it was not followed and reported the limestone powder. The hydration of major phases of cement,
in more details. In this part, we are making the discussions towards the calcium silicate phases (C3S, C2S), starts from about 10 h and
that. From the hydration heat flow rate and total heat of hydration continues until a long period of time, shown in Fig. 19-a. From
shown in Fig. 19, both composite cement pastes with the additional hydration heat development, seashell powder applies a better hy-
minerals developed higher hydration heat flow rate and total heat dration enhancement for the calcium silicate phases than the
of hydration than the pure cement paste. This reveals the enhanced limestone powder.
cement hydration by each of the two powders when used as an Figs. 20 and 21 report the rheological properties (viscosity and
additional additive. Between them, seashell powder appears more dynamic yield stress) of the fresh composite cement pastes and the

Fig. 19. Hydration heat development of the composite cement pastes with additional seashell powder and limestone powder processed based on the weight of OPC: (a) hydration
heat flow rate and total heat of hydration during 72 h hydration, (b) hydration heat flow rate within the first hour.
248 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

Fig. 20. Viscosity and dynamic yield stress of the OPC paste, composite OPC pastes with additional bio-CaCO3, and geo-CaCO3, respectively.

suspensions. Between seashell powder and limestone powder, the

viscosity and dynamic yield stress of the composite cement paste
with seashell powder are less than that with limestone powder.
One direct reason can be owing to the smaller average particle size
of limestone powder (5 mm) than that of seashell powder (60 mm),
shown in Fig. 1. Secondly, the surface area of seashell powder and
limestone powder also plays important roles. Although the surface
area of seashell powder is larger than that of limestone powder, the
density of seashell powder is also greater than that of limestone
powder. Between the same volume of composite cement pastes
with seashell powder and limestone powder, the composite
cement paste with seashell powder contains clearly less volume of
seashell powder than the one with limestone powder. Combining
the two aspects, the total surface area (that affects the water de-
mand) may still be less in the composite cement paste with seashell
powder than that with limestone powder.
For compressive strength of the hardened composite cement
pastes, the additions of both powders clearly improved this me-
Fig. 21. Compressive strength of the hardened mixtures of the OPC paste, composite chanical property. However, the improvement of seashell powder
OPC pastes with additional bio-CaCO3, and geo-CaCO3, respectively. was evidently higher than that of the limestone powder, shown in
Fig. 21. Again, this can be owing to the higher surface area and
chemical reactivity of seashell powder than that of limestone
powder.
According to FTIR analysis in Fig. 22, major types of phases are
qualitatively similar in the hydrated composite cement paste with
each of the two minerals. The peak positions for the two calcium
carbonate minerals are slightly different, which might stem from
the different crystal structures of bio-CaCO3 and geo-CaCO3 in
seashell powder and limestone powder. To quantify approximately
the reactivity of seashell powder and limestone powder in the
composite cement paste, thermogravimetric analysis (TGA) was
conducted on the hydrated samples hydrated for 7 days, with the
results shown in Fig. 23. The decomposition peaks (Fig. 23 left) and
weight loss curves (Fig. 23 right) together demonstrate the quan-
titative information of hydration products and degrees in the
composite cement pastes with seashell powder and limestone
powder. Seashell powder promotes a higher degree of hydration in
the composite cement paste than the limestone powder. The
number of hydration products (e.g. ettringite, AFm, portlandite)
Fig. 22. FTIR spectra of hydrated (7-day hydration) OPC paste, composite OPC pastes developed in composite cement paste is notably greater with
with additional bio-CaCO3, and geo-CaCO3, respectively.
seashell powder than limestone powder, meaning that seashell
powder participates at and promotes the hydration of cement in a
more profound way than limestone powder.
compressive strength of the hardened composite cement pastes Based on TGA data on carbonates, the following calculations
with seashell powder and limestone powder, respectively. For specifically show the consumption of each calcium carbonate
rheological properties, the additions of both powders increased the mineral (bio-CaCO3 and geo-CaCO3) in the corresponding com-
viscosity and dynamic yield stress of the composite cement pastes, posite cement paste with seashell powder and limestone powder,
mainly due to the increase in the overall solid content in the fresh respectively. First, the weight loss due to CaCO3 decomposition was
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 249

Fig. 23. Thermogravimetric decomposition peaks (left) and weight loss (right) for the hydrated (7-day hydration) OPC paste, composite OPC pastes with additional bio-CaCO3, and
geo-CaCO3, respectively.

10% for composite cement paste with bio-CaCO3 and 9.8% for that morphologies of the hydration products developed in the hydrated
with geo-CaCO3, and 3% for pure cement paste. Therefore, the composite cement pastes with seashell powder and limestone
remaining CaCO3 in each of the hydrated (7-day hydration) com- powder. More attention was paid to the ettringite and calcium
posite cement pastes can be obtained respectively in the following, carboaluminate phases because the two phases were closely
that is, for the composite cement paste with bio-CaCO3: 10%- related to the chemical reactivity of calcium carbonate mineral in
(3%  0.8) ¼ 7.6%, and with geo-CaCO3: 9.8%- (3%  0.8) ¼ 7.4%. cement hydration. Although the two phases (ettringite and calcium
Now, we continue to calculate the original CaCO3 content in carboaluminate) were similar in morphologies in the two hydrated
each composite cement paste at time 0, and then we can get the cement matrixes, they tended to be more consistent in terms of
content of CaCO3 consumed during the 7-day hydration by sub- size, orientation, and spatial arrangement in the hydrated cement
tracting the remaining content of CaCO3 after 7-day hydration matrix with seashell powder than limestone powder. Besides, their
(obtained above) from the original CaCO3 content. The calculation locations seemed to be different in the two hydrated cement ma-
of original CaCO3 content at time 0 in the composite cement paste trixes. Some amounts of ettringite and calcium carboaluminate
relates to the purity of CaCO3 in seashell powder and limestone phases were found close to and in the vicinity of various spherical-
powder (which was measured and presented in Fig. 1), also to the shaped clusters. These clusters were further confirmed to be the
amount of water infused into the hydrated cement paste (which seashell powder particles surrounded by and connected to cement
was calculated by the theoretical w/c ratio of 0.23 for the chemically hydrates, such as the CeSeH gel. Major elemental compositions of
bonded water within the hydrated cement paste). Thus, the CaCO3 the cluster included aluminum (Al), sulfur (S), sodium (Na), and
content at time 0: (0.2  95.5%)÷ (1 þ 0.8  0.23) ¼ 16.1% for the chloride (Cl), together with calcium (Ca) and silicon (Si). The ele-
composite cement paste with bio-CaCO3, and (0.2  86.4%)÷ ments of Al and S suggested the existence of ettringite. Seashell
(1 þ 0.8  0.23) ¼ 14.6% for the composite cement paste with geo- powder also contained little amount of Na and Cl from seawater.
CaCO3 paste. Fig. 24 shows the content of CaCO3 consumed during The presence of Ca and Si can be related to the hydrated calcium
the 7-day hydration for bio-CaCO3 and geo-CaCO3. Seashell powder silicate phase (CeSeH gel). The hydrated cement matrix with
(bio-CaCO3) was consumed more during the cement hydration, and limestone powder did not demonstrate morphologies of limestone
appeared to be more reactive in the composite cement paste than particle surrounded by cement hydrates. Instead, it seemed similar
limestone powder (geo-CaCO3). to the hydrated matrix of pure cement, and presented no clear
Through SEM observation, Fig. 25 demonstrates surface morphologies of hydration products developed with limestone
powder. These phenomena can suggest that seashell powder has
evidently higher chemical reactivity and physical roles (e.g. particle
morphologies of seashell powder shown in Fig. 2) than limestone
powder in the same cement system.
Fig. 26 shows the nano-structure (observed by TEM) of the
CeSeH matrix phases developed in hydrated cement matrix with
bio-CaCO3, geo-CaCO3, and pure OPC paste, respectively. Many
nanosized clusters (5e10 nm), appeared as the black dots in the
image, were found embedded throughout the CeSeH matrix
phases developed with bio-CaCO3. Based on the element mapping
coupled with TEM, Fig. 27 demonstrates that the distribution of the
nanosized clusters is generally consistent with the distribution of
Na and Cl in the CeSeH matrix phases with bio-CaCO3. In previous
discussion, we confirmed that Na and Cl are derived from the
seawater environment and are present in the seashell powder.
Thus, the nanosized clusters can be the crystalline substances
corresponding to the products of cement hydration involving
seashell powder. Therefore, based on this study, seashell powder
Fig. 24. Reactivity of seashell powder (bio-CaCO3) and limestone powder (geo-CaCO3) perhaps undergoes a dissolution and precipitation process in the
in the composite cement paste: amount of CaCO3 at time 0 and time 7 days, and the high alkaline hydrating cement environment. The seashell powder
amount of CaCO3 consumed during the 7-day hydration, results based on the weight can be firstly dissolved in the hydrating medium, and dissociated
percentage in the composite cement paste.
250 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252

Fig. 25. Surface morphologies of the hydrated cement matrix with seashell powder (bio-CaCO3) and limestone powder (geo-CaCO3); the bottom left image showing the elemental
composition of the square insert area (the spherical-shaped clusters) at the hydrated cement matrix with bio-CaCO3 in the top left image.

Fig. 26. TEM images of the CeSeH matrix phases for the OPC paste, the OPC paste with bio-CaCO3, and the OPC paste with geo-CaCO3.

into calcium and carbonate which then participated at the hydra- the fresh mixtures can be reduced by about 7%, 20%, 33%, and
tion of cement. The specific hydration products corresponding to 50%, when seashell powder is used to replace 5%, 10%, 20%, and
this process can be the observed new crystalline phases (nanosized 40% of cement, respectively in the blended cement. The
clusters) widely dispersed into the hydrated CeSeH matrix phases, dispersion and dilution effects of seashell powder in the
such as the new precipitated nanosized crystals of CaCO3 and cal- blended cement mixtures serve as the main reasons. When
cium carboaluminate phases. These nanosized clusters haven't seashell powder is used in blended cement, the w/c ratio (water
been observed in the CeSeH matrix phases developed with geo- demand) can thus be effectively reduced to meet the workability
CaCO3 and pure OPC, and they are believed to modify and reinforce requirements.
the hydrated CeSeH phase, the most important and dominant 2) Waste seashell powder can reduce the hydration heat release
constituent in the hydrated cement matrix from the nanoscale (hydration heat flow rate and total heat of hydration) in the
level, e.g. the enhanced compressive strength developed with blended cement mixtures. The total heat released in the blended
seashell powder over the ones with geo-CaCO3 and pure OPC. cement mixtures during 72 h hydration can be reduced by about
3%, 5%, 12%, and 30% when seashell powder is used to replace 5%,
4. Conclusions 10%, 20%, and 40% of cement. The decrease in hydration heat
release is mainly due to the reduction in cement content in the
The following points are the conclusions of this work, on recy- blended cement with seashell powder. The hydration heat
cling waste seashells with Portland cement to produce sustainable development (in terms of cement only) increases with the in-
cementitious materials: crease of seashell powder in the blended cement mixtures,
indicating the cement hydration enhancement by seashell
1) The use of waste seashell powder in blended cement can powder. The dispersion and nucleation effects of seashell
improve the workability of the fresh mixture. The viscosity of powder promote the hydration process of cement. Seashell
 J. Wang et al. / Journal of Cleaner Production 220 (2019) 235e252 251

Fig. 27. Element mapping of the CeSeH matrix phases for the cement paste with (a) bio-CaCO3, and with (b) geo-CaCO3.

powder also participates at chemical reactions within the hy- Biological calcium carbonate (seashell powder) exhibits more
drating cement system to form new hydration products, pronounced physical and chemical effects in cement system
contributing further to the hydration heat development. than geological calcium carbonate (limestone powder).
3) The XRD and SEM analyses show that ettringite and calcium 7) The recycling of waste seashells with cement can be a cleaner
carboaluminate coexisted in the hydrated blended cement sys- production solution for the green biological solid waste man-
tem, and their amounts increased with the increase of seashell agement and the sustainable cementitious materials develop-
powder in the blended cement. Some amounts of ettringite and ment, when waste seashells (or similar biological solid wastes)
calcium carboaluminate phases were found close to and in the are recycled in the powder form and reused as a renewable
vicinity of various spherical-shaped clusters which were further alternative to the non-renewable limestone powder.
confirmed to be the seashell powder particles surrounded by
and connected to cement hydrates. Seashell powder enhanced Acknowledgements
the formations of hydration products, such as ettringite, calcium
carboaluminate, and portlandite. The authors thank New York University Abu Dhabi (NYUAD) for
4) In order to clearly see roles of seashell powder in blended providing the financial and facility support to perform this research
cement, the w/c ratio (water content) needs to be correspond- work. Special thanks also go to colleagues from NYUAD core tech-
ingly reduced when the seashell powder is used to replace nology platforms who provided us with their insights and expertise
cement in the blended cement mixtures. When used as addi- in the analytical and materials characterization work.
tional additives rather than the cement replacement, both
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