Construction and Building Materials 346 (2022) 128247

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Construction and Building Materials

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

Leveraging internal curing effect of fly ash cenosphere for alleviating

autogenous shrinkage in 3D printing
Jie-Lin Tao a, b, Can Lin a, b, Qi-Ling Luo a, Wu-Jian Long a, *, Shu-Yi Zheng a, Chen-Yu Hong a
a
Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, Shenzhen Durability Center for Civil and Transportation Engineering, Key Lab of
Coastal Urban Resilient Infrastructure, MOE, College of Civil and Transportation Engineering, Shenzhen University, Shenzhen, Guangdong 518060, PR China
b
Department of Structural Engineering, College of Civil Engineering, Tongji University, Shanghai 200092, China

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

Keywords: The development of three-dimensional (3D) printing technology in the construction industry has coincided with
3D printing growing attention on the investigation of printable cement-based composite. Meanwhile, the exploitation of
Limestone calcined clay cement high-performance and environmentally friendly printable cement-based composite is an inevitable path for the
Fly ash cenosphere
sustainable development of 3D printing in the construction industry. This study proposes the use of perforated fly
Autogenous shrinkage
Rheology
ash cenospheres (PFACs) as internal curing (IC) agent into limestone calcined clay cement (LC3) mortar to
develop a novel green printable cement-based composite. Rheological behavior of LC3 mortar containing PFACs
has been shown to meet the requirements of 3D printing. The internal curing effect on autogenous shrinkage of
mortar was studied by employing Fiber Bragg Grating (FBG) technology. Compressive and flexural strengths of
LC3 mortar containing PFACs were evaluated. Additionally, microstructural investigation was analyzed through
SEM, and the hydration products were studied by XRD and TG tests. Results suggest that shrinkage strain of LC3
mortar containing 15% PFAC was approximately 80% lower than that of mortar without PFAC, which indicates
that PFAC in LC3 mortar can be effective in holding the mixing water for IC that can reduce the autogenous
shrinkage. Furthermore, additional mechanical strength of mortar containing PFAC was generated through IC
effect and the pozzolanic activity of PFAC, which can effectively compensate the strength loss caused by the
PFAC. However, microstructural investigation indicated that the pozzolanic activity of PFAC has limited effect on
cement hydration compared with the introduction of additional IC water. Consequently, this study reveals that it
is effective to adopt PFAC as IC agent into LC3 mortar to develop high-performance and sustainable printable
cement-based composite.

1. Introduction
The construction industry is moving towards digitalization and
intelligentization, thus increasing the possibility of using three-
dimensional (3D) printing in concrete construction[1,2]. Sustainable
development of 3D printing technique in construction industry is closely
related to the development of environmentally friendly printable
cement-based composites. Limestone calcined clay cement (LC3), which
replaces 50% of the ordinary Portland cement (OPC) in the binder
composition by using calcined clay and limestone, has been proved to be
an effectively environment-friendly material [3]. Furthermore, LC3
greatly combines the advantages of calcined clay and limestone and has
excellent potential in 3D printing [4,5]. According to the study by
Muzenda et al., calcined clay causes an increase in thixotropy, plastic
viscosity, shear yield stress, cohesion and adhesion [6,7]. The use of
limestone can slightly reduce these parameters and therefore can help
enhance the flowability of LC3 [8]. Combining the technologies of green
LC3 material and 3D printing can be a potential method to promote
sustainability and digitalization in the construction industry.
Generally, extrusion is the main implementation method in 3D
printing concrete technology, which forms a designed construct intricate
3D objects that are cast layer-by-layer without the need of a formwork
system. Issues with inter-layer quality can hinder the performance of
printed elements in the extrusion-based 3D printing process. Potential
defects can be created in the interface, which can induce stress con­
centration [9,10]. Consequently, interlayer bond of printed objects has
garnered particular attention with regard to the structural performance
of 3D printed concrete. The bond strength of printed objects is a function

* Corresponding author.
E-mail address: longwj@szu.edu.cn (W.-J. Long).

https://doi.org/10.1016/j.conbuildmat.2022.128247
Received 22 April 2022; Received in revised form 12 June 2022; Accepted 22 June 2022
Available online 11 July 2022
0950-0618/© 2022 Elsevier Ltd. All rights reserved.
J.-L. Tao et al. Construction and Building Materials 346 (2022) 128247

Table 1
Chemical composition of different raw materials (mass %) from XRF.
Chemical composition SiO2 Al2O3 Fe2O3 CaO MgO K2O SO3 Na2O TiO2 LOI

OPC 19.96 4.35 3.50 62.89 2.90 0.80 3.30 0.48 1.30
CC 64.19 28.50 0.62 0.32 0.16 0.26 0.11 0.40 5.33
LP 12.48 3.64 2.53 46.17 1.98 0.60 0.61 31.98
SF 92.26 0.89 1.97 0.49 0.96 1.31 0.33 0.42 3.47

of several parameters including aggregate size, viscosity of printing
materials, and various printing parameters [11]. It is worth noting that
bond strength between layers also depends on surface moisture condi­
tions [12]. Particularly, evaporation of free water in printing materials
can induce a negative pressure in the pore system, thus causing
shrinkage. Restraining such early-age shrinkage can results in interlayer
bond and lead to cracking, which can reduce the interlayer bond
strength [13]. Furthermore, if the hydration rate is not fast enough to
consume the free water, evaporation can occur, resulting in rapid water
loss [14]. Hence, maintaining high internal relative humidity to control
moisture loss in printing materials is key to enhance interlayer bond
strength [15].
Autogenous shrinkage is one of the main threats caused by moisture
loss at early age. It starts immediately after mixing and is related to the
outward transport of moisture [16,17]. After the layer-by-layer printing
process, due to the absence of formwork, both the sides and the interface
between printed layers are directly exposed to the environment,
resulting in faster water evaporation of cement-based material surfaces
than traditional construction methods with a formwork system [16].
Water loss can develop capillary pressure due to the accumulation of
water menisci in capillary pores when the free water content at the
surface is insufficient and cannot maintain high relative humidity at
exposed surfaces. As a result, this pressure can cause capillary tensile
stresses, which can lead to shrinkage and eventually cracking [18,19].
The rate and extent of autogenous shrinkage are affected by a variety of
factors that have an effect on the moisture content of the mixture. In
addition to the humidity, temperature, and air flow of the external
environment [20], shrinkage is greatly related to the moisture condition
of the printing material.
Shrinkage mitigation can involve the use of saturated lightweight
sand (LWS) or superabsorbent polymers (SAPs) for internal curing (IC).
IC can be effective to maintain the relatively high internal moisture
content in cement-based materials. For instance, Meng et al. [21] ach­
ieved autogenous shrinkage reduction and mechanical strength
enhancement by applying LWS. Ma et al. [12] found that the use of
cellulose fiber as IC agent could hold water to accelerate hydration and
improve bond and mechanical properties while alleviating shrinkage
and porosity. Van Der Putten et al. [13] studied the application of SAPs
in cement-based mortar for 3D printing, and proving the efficiency of
SAP for reducing shrinkage deformations of the mortar. Based on the
previous studies, autogenous and unprotected shrinkage are mitigated
up to 200% by the addition of SAPs. Although these two materials have
excellent performance in IC, it has been found that they have adverse
effects on mechanical properties. For example, when 0.3% addition of
SAP is added, the compressive strength of concrete decreased by about
10% at 28 days [22]. It’s worth noting that 3D printing construction
usually takes place under outdoor conditions, and the specific surface
area of the printed components is larger than that of ordinary casting
components, and it is more prone to moisture loss, so the role of IC in 3D
printing is more significant.
Fly ash cenospheres (FAC) are hollow fly ash particles generated in
coal burning power plants. Such FAC can be used as an IC agent without
degrading mechanical strengths because of the hard pozzolanic
aluminum silicate shell [23]. As Chen et. al. Reported, internal curing

100

80

60

40

20

0
0.01 0.1 1 10 100

Fig. 1. Particle size distribution of difference raw materials.

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J.-L. Tao et al. Construction and Building Materials 346 (2022) 128247

Fig. 2. SEM images of (a) original FAC and (b) perforated FAC.

2. Materials

The LC3 composite consists of calcined clay (CC), limestone powder

Fig. 3. XRD pattern of original FAC and perforated FAC.
with FAC can not only eliminate the autogenous shrinkage of alkali
activated slag mortars, but also significantly improve the compressive
strength (16.2%–28.9%) over the control sample at 56 days thanks to
the reactivity of FAC. In addition, since the hollow structure inside the
FAC, water can be loaded into and released easily [24]. The water
released inside the composites can maintain a relatively high relative
humidity to prevent self-desiccation.
The present investigation is intended to develop a novel LC3-based
mortar for 3D printing that incorporates FAC. The effectiveness of FAC
as an IC agent was evaluated by determining its influence on interlayer
bonding was verified through monitoring autogenous shrinkage using
FBG technique. The rheological behavior, mechanical properties, and
autogenous shrinkage stress, and cracking of the material for 3D printing
were investigated. Moreover, the SEM based microstructural investiga­
tion was used for evaluating the morphology of FAC in mortars before
3D printing. Matrix bonding and observation of hydration products were
aided by X-ray diffraction (XRD) and Thermal Gravity Analysis (TGA).
(LP), ordinary Portland cement (OPC), and silica fume (SF). A Type I
ordinary Portland cement (OPC; 52.5R) was used in this study, which
conforms to the requirements of the Chinese Standard GB 175 [25]. A
commercially available FAC was used. Table 1 shows the chemical
composition of the materials. The FAC has a size range of 10–150 μm.
The FAC is hollow and is basically closed. Fig. 1 shows the particle size
distribution of various raw materials. A Gemini scanning electron mi­
croscope (SEM, 300-71-11) was used to characterize the morphology of
the FAC, as shown in Fig. 2(a). In addition, a polycarboxylate-based
high-range water-reducing admixture (HRWRA) was used to enhance
the flowability of the fresh cement-based composites. And the ISO
Standard Sand in accordance with Chinese standard (GB/T 14684) was
used in this study.
In order to make the interior of the FAC accessible to water, part of
the enclosure needs to be removed. Acid treatment was used for this
purpose [26]. First, FAC were soaked into 1.0 M NH4F-1.2 M HCl-H2O
solution for 2 h with occasional stirring. When more than 95% of the
FAC sinks to the bottom of the container, the perforation is considered to
be completed. Subsequently, the perforated FAC was vacuum filtered,
rinsed with 1500 mL water, and dried in an oven at 110 ◦ C for 8 h. The
morphology of the perforated FAC (PFAC) is shown in Fig. 2(b). Addi­
tionally, X-ray diffractometer was applied to identify the various
mineralogical phases of the FAC and PFAC, as shown in Fig. 3.
3. Test methods
3.1. Mixture proportions and test procedures
Based on an improved LC3 material that we have previously devel­
oped that is more suitable for 3D printing [27], The substitutions of OPC
were made at a total level of substitution of 55%, including 50% of CC
and LP, and 5% SF. The ratio of calcined clay to limestone was main­
tained at 2:1. The additions of FAC/PFAC were 15 and 30 vol%. The

Table 2
Mixture proportions of mortars used in this study.
Mix. ID OPC CC LP SF Sand FAC PFAC w/b HRWRA

LC3-FAC0% 45 33.3 16.7 5 250 – – 0.48 0. 4

LC3-FAC15% 45 33.3 16.7 5 212.5 11.2 – 0.48 0. 4
LC3-FAC30% 45 33.3 16.7 5 175 22.5 – 0.48 0. 4
LC3-PFAC15% 45 33.3 16.7 5 212.5 – 11.2 0.48 0. 4
LC3-PFAC30% 45 33.3 16.7 5 175 – 22.5 0.48 0.4

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J.-L. Tao et al.
Fig. 4. Rheology test protocol.
water-to-binder ratio (w/b) was maintained at 0.48, and the HRWRA
accounting for 0.4 wt% of the total binder was added in each mixture for
ensuring sufficient printability. The ratio of aggregate to binder is kept
at 2.66 by volume. Specifically, in order to achieve IC effect, the PFAC
were blended with the calculated weight of water (including IC and
mixing water). The mixture of PFAC and water, HRWRA, sand and
binder are then mixed together following the ASTM C305. The different
mortar prepared for this study are shown in Table 2, and the mix.ID was
named according to different dosage of FAC/PFAC in LC3 mortar.
3.2. Water absorption test
Water absorption of perforated and un-perforated FAC is closely
related to its pore size and surface perforation distribution. Effective
internal curing of FAC needs appropriate surface perforation distribu­
tion. Large perforation size means rapid saturation but poor water
retention capacity. Even if water can be absorbed through small pores, it
is difficult to release for IC. The weight change of saturated surface dry
(SSD) FAC/PFAC was measured to evaluate the desorption behavior
under a fixed relative humidity (RH) of 94% [28]. The SSD PFAC was
obtained according to ASTM C128 [29]. The RH of 94% simulates the
moisture condition inside of cement-based composites. First, the FAC
and PFAC were separately mixed with water and stirred until most of the
PFAC sank at the bottom of the container, and then were filter out. The
weight of the sample was recorded every 15 min. After the weight of
Fig. 5. Working principle of FBG sensor.
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Construction and Building Materials 346 (2022) 128247
sample was equilibrating, it was dried at 110℃ for 48 h, and the dry
weight of the sample was then calculated.
3.3. Rheological test
Three protocols were adopted for analyzing different rheological
properties of the mortar mixtures. Rheology of printable composites
refers the evaluation of the thixotropy, yield stress, and plastic viscosity
of the mortars to reach the desired printability and buildability. The
rotating viscometer (unlimited number of speeds between 0.3 and 1500
rpm) was used to measure the rheological properties of printable
materials.
Flow curve test was conducted using three difference rheological
protocols, as shown in Fig. 4. Dynamic yield stress and plastic viscosity
of the mortar mixtures were assessed by increasing the shear rate from
0 to 100 s− 1 in 60 s and then decreasing it from 100 to 0 s− 1 in 60 s [27].
The static yield stress of the tested mortars was determined using the
shear growth approach at a constant shear rate of 0.1 s− 1. In addition,
the structural recovery was used to reflect the thixotropy of printable
mortars, which was defined as structural re-building rate of the fresh
mortar after removing the applied shear stress. The structural recovery
was obtained by adopting three different shear rates (i.e., (a) 0.01 s− 1 for
60 s, (b) 300 s− 1 for 30 s, and (c) 0.01 s− 1 for 60 s) and recording the
difference in apparent viscosity values [30].
J.-L. Tao et al.
Fig. 6. Position of the FBG sensor in 3D printing project.
3.4. Preparation and installation of the fiber Bragg Grating sensor in 3D
printing process
In this study, the 3D printed samples were realized by the vertical
stacking of filament layers, which was a six-layer linear structure with a
length of 45 cm. The printing nozzle is circular nozzle with a diameter of
20 mm, moving speed of nozzle is 20 mm/s, and the extrusion rate is 0.5
revolutions per minute (rpm). In addition, the printing temperature of
each sample is controlled at 25 ± 5 ◦ C.
The FBG sensor was used to monitor internal strain and temperature
of printed structural during 3D printing process. The working principle
of FBG sensor is presented in Fig. 5 [31]. Due to the injected light with a
broadband can interfere at the grating location, the transmitted and
reflected lights are motivated. The shift of central Bragg wavelength (Δλ
λ )
is linearly related to the change of strain or temperature. The expression
of Δλλ is as follows:
Δλ ( )
= 1 − peff Δε + (α + ξ)ΔT
λ
where λ is central Bragg wavelength of FBG sensor, Δλ is shift of central
Bragg wavelength of FBG sensor, ΔT is variation of temperature in FBG
sensor, and Δε is strain variation of FBG sensor, respectively. The α, ξ,
and peff are thermal expansion index, thermal-optic index, and photo-
elastic index, respectively.
In order to avoid the influence of bending structure on shrinkage
cracking, this study adopted linear printed samples of 45 cm length with
six printing layers. One strain sensor fiber is placed in two layers, each
fiber contains three of uniform distribution strain sensors. Meanwhile, a
temperature sensor was placed in the middle of the third layer. Multiple
points can be measured simultaneously through the series of sensors.
The FBG sensor is evenly placed between the layers during the 3D
printing process. After printing, a rigid cracking inducer was gently
inserted on the top of printed object. All experiments were carried out
indoors at a temperature of 25 ± 5 ◦ C and relative humidity of about
60%. Two independent fans were used to generate a uniform wind speed
of 13 ± 1 km/h on the printed sample. The employed wind speed is
defined as a mild breeze in the Beaufort wind speed guide [15], simu­
lating the printing environment under moderate wind speed conditions.
The position of FBG sensors during printing process is presented in
Fig. 6.
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Construction and Building Materials 346 (2022) 128247
3.5. Mechanical properties
Mechanical test was conducted to evaluate the mechanical proper­
ties of cement-based composites [32]. The compressive and flexural
strengths of the samples were measured at 28 days by the computerized
electronic universal testing machine.
3.6. Chemical structure analysis test
The effect of PFAC/FAC on the hydration products was evaluated by
XRD analysis with Cu_Ka radiation at 40 kV and 40 mA. The scan scope
and speed were 2θ = 5◦ ∼ 70◦ and 0.1 s/step, respectively.
Moreover, the phase transition and weight change with temperature
were analyzed by thermogravimetric (TG) at a temperature range from
30 ◦ C to 1000 ◦ C and a heating rate of 10 ◦ C/min under a nitrogen
atmosphere.
The XRD and TG samples were prepared by cutting predetermined
age mortar into small pieces and soaking in anhydrous ethanol for
stopping hydration. Then, sample was ground and filtered using a 200
mesh sieve to yield particles smaller than 75 μm.
3.7. Microstructure evaluation
In order to explore the effect of PFAC on the microstructure of the
LC3 cement-based composites, the 1×1×1 cm samples were broken after
standard curing for a certain age (3, 7 and 14 days) and used for
microstructural test. A Quanta FEG 250 Scanning Electron Microscope
(SEM) was used to explore the microstructure of broken samples. The
operating voltage is 20 kV, and the image resolution is 1280×960 pixels.
4. Results and discussion
4.1. Desorption behavior of perforated cenosphere
The desorption behavior of the IC agent determines the effect of IC
water, which mainly depends on their characteristic such as pore
structure of lightweight aggregate or molecular structure of superab­
sorbent polymers. The IC water content and its release time are the main
key factors for relieving the autogenous shrinkage of cement-based
composites. For evaluating the IC effect of FAC in LC3, the pre-
absorption FAC and original FAC were studied for water desorption
J.-L. Tao et al.
140
PFAC
120 FAC
Moisture content (%)
100
80
60
40
20
0
0 1 2 3 4 5 6 7 8 9
Time (h)
Fig. 7. Desorption behavior of FAC and PFAC.
behavior. As shown in Fig. 7, the pre-absorption FAC achieved equi­
librium in nearly 9 h, while the original FAC achieved equilibrium
appropriately in 3 h. At equilibrium, about 100% of the loaded water
was released from the FAC. Results show that it is effective in retarding
the water loss in this period for taking pre-absorption FAC as an IC agent
since the autogenous shrinkage in cement-based composites were found
to mostly occur during the hardening process [24].
4.2. Rheological behavior
The rheological behavior of LC3 mortars containing different dos­
ages of FAC/PFAC was tested. Plastic viscosity and dynamic yield stress
of the FAC/PFAC modified LC3 mortars were measured by fitting the
non-linear descending flow curve using the Bingham model, as shown in
Fig. 8(a). The R-square of all tested mortars were above 0.9.
In Fig. 8(a), the plastic viscosity and dynamic yield stress of the
mortar containing 15% FAC are similar to those of the control mortar.
The mortar containing 30% FAC had higher rheological parameters.
This is due to the competition of ball effect and the large specific surface
area of the FAC. On the one hand, the spherical morphology of the FAC
has a positive effect on flowability of the mortar. The “ball-bearings”
effect of the FAC increased the water film thickness of cement particles,
hence reducing the plastic viscosity and dynamic yield stress of LC3
Fig. 8. Rheological behavior of cement-based composites with different FAC dosage: (a) plastic viscosity and dynamic yield stress; (b) static yield stress and
structural recovery.
Construction and Building Materials 346 (2022) 128247
mortars are decreased. It helps in mortar printing process, where there is
sufficient flowability to ensure success extrusion. On the other hand, the
total specific surface area of mortar is increased when parts of fine ag­
gregates were replaced by FAC, due to the particle size of FAC is between
cementitious material and fine aggregate. When the amount of FAC is
small, the “ball-bearings” effect of the FAC plays a dominant role, and
the dynamic yield stress of mortar is decreased. When high content of
FAC is added, the specific surface area plays a dominant role, the water
film thickness on the particle surface is decreased, and the dynamic yield
stress is increased.
According to Baenes’s theory [33], the viscosity of suspension is
mainly affected by the electrostatic force, van der Waals force, and
Brownian motion among particles at the micron scale, while it is mainly
affected by the collision and friction between particles above the micron
scale. Therefore, when FAC is used as a partial replacement of fine
aggregate, its plastic viscosity is mainly changed by the collision and
friction between particles. Compared with the irregular surface
10 morphology and particle shape of natural sand, FAC is smooth and
spherical. The friction force between particles is decreased when FAC is
used to replace part of the sand, thus decreasing the plastic viscosity.
However, when the replacement rate of the FAC increases to 30%, the
particle packing of the system increase gradually. Although the surface
friction caused by FAC is small, the increase of the packing density in­
creases the number of contact points between particles, leading to the
increase of plastic viscosity.
Additionally, it can be seen from the figure that the rheological
properties of mortars made with PFAC are lower than those containing
ordinary FAC. This is because the PFAC can release water outward under
shear stress in the rheological testing process, which increases the
lubrication between the binder particles.
Fig. 8(b) shows the static yield stress and structural recovery rate of
various mixtures. Structural recovery rate is the viscosity recovery rate
of the mortar before and after high-speed shear. In Fig. 8(b), the static
yield stress of mortars made with and without FAC is shown to be
similar, and only decreases slightly when the PFAC is used. The results
indicate that the IC water in the PFAC can be released under low shear
rate. Comparing the structural recovery of various mortars, the addition
of FAC and PFAC can decrease the structural recovery of the mortar. This
can be explained by the “ball bearing effect” of the FAC and PFAC. In
addition, the released water from the PFAC further reduces the struc­
tural recovery.
4.3. Autogenous shrinkage stress and cracking
Bragg wavelength obtained by FBG sensor was converted into strain,
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J.-L. Tao et al. Construction and Building Materials 346 (2022) 128247

Fig. 9. Variation of strain with time between layers in printing sample.

and the variation of strain caused by autogenous shrinkage in 3D printed
samples were obtained, as shown in Fig. 9(a and b). In each group of
samples, one FBG fiber is placed on the second and fourth layers, and
each fiber contains 3 measuring points, which are marked as ①, ②,③,
④, ⑤and ⑥. According to Moelich et al. [16], when a rigid crack
inducer is placed above the printed sample, the sample would first un­
dergo a slight contraction displacement towards its center before
cracking, and a few minutes later, the stress direction can change and
begin to shift towards the sides. As shown in Fig. 9(a), similar to the
previous research, the measuring points ② and ⑤ in the middle of the
samples that have different stress directions with other points. It means
that the measuring points in the middle are subjected to tensile stress,
while the left and right points are subjected to compressive stress. This is
consistent with the experimental results in the literature [16]. It is
mainly due to the three constraint points by the rigid crack induction
device placed, which divides the sample into two parts, as shown in
Fig. 9(c). In the hardening process of the two samples, two parts of
mortar contracted to its center respectively in 5 h, and the central
measuring points ② and ⑤ were subjected to tensile stress as positive
strain, while the measuring points ①, ③, ④ and ⑥ on the two sides were

Fig. 10. Original and binary images of the crack on specimens with different mixtures: (a) LC3-PFAC0%; (b) LC3-FAC15%; (c) LC3-PFAC15%.

7
J.-L. Tao et al.
Compressive strength (MPa)
Fig. 11. Mechanical strengths of mixtures at 28 days: (a) compressive strength and (b) flexural strength.
subjected to compressive stress as negative strain.
It is also observed in Fig. 9(b) that the mortar mixed with PFAC has a
smaller autogenous shrinkage strain. Comparing the strain at location ⑤
of the two samples (LC3-PFAC0% and LC3-PFAC15%), it can be
concluded that the shrinkage strain of mortar mixed with PFAC is
reduced by about 81% compared to that without PFAC. This indicates
that PFAC has good IC effect on mortar. When the moisture inside the
system is lost by the environmental factors, PFAC releases water out­
ward in time due to the absorption of water by capillary, and the
autogenous shrinkage of samples can be reduced. Therefore, the use of
PFAC with IC water can effectively reduce the autogenous shrinkage of
LC3 composites in 3D printed objects.
Furthermore, the development of autogenous shrinkage cracks on
sample containing 15% FAC/PFAC and sample made without PFAC
were comparatively analyzed to further explore the effect of PFAC on
printing interlayer, as shown in Fig. 10. It can be seen that the cracks in
the samples containing 15% FAC and no PFAC extend horizontally be­
tween layers. Due to the poor interlayer bonding of these two groups, the
cracks are shown to develop at the interlayer and then propagate in the
horizontal direction along the fragile interfacial zone. However, the
autogenous shrinkage crack of the sample containing 15% PFAC
developed in the vertical direction all times. This can be associated with
the fact that IC can improve the interlayer adhesion of 3D printed
components [12]. The PFAC can retain moisture and promote the hy­
dration between the layers, thereby enhancing the adhesion and
reducing shrinkage and porosity that are critical to enhance the quality
of the interlayer in 3D printing. Moreover, comparing the depth of
cracks, it can be found that the introduction of PFAC reduces the depth
of autogenous shrinkage cracks. This is also because the IC effect of
PFAC can effectively enhance the interlayer bonding of 3D printed
components and inhibit the development of autogenous shrinkage
cracks at early age.
4.4. Mechanical performance
Since FAC/PFAC consists of hollow cenospheres, it is important to
determine whether its IC effect can compensate for the strength loss
caused by this inherent porosity. The FAC also has a lower elastic
modulus than quartz sand, hence partial substitution of the sand can
lead to reduction in mechanical properties [34,35]. Therefore, it is
important to investigate the effect of FAC/PFAC on mechanical prop­
erties of LC3 composites. Fig. 11 shows the 28-day compressive and
flexural strength of the investigated LC3 composites.
As shown in Fig. 11, the 28-day compressive strength of the mortars
8
Construction and Building Materials 346 (2022) 128247
Flexural strength (MPa)
with the addition of FAC ranged between 37.5 MPa and 48.3 MPa, and
28-day flexural strength ranged between 6.5 MPa and 8.3 MPa. The 28-
day compressive strength of the mixtures made with 15% and 30% FAC
mortar decreased by 17% and 22%, respectively, compared with the
control group (LC3-PFAC0%). Moreover, the flexural strength decreased
by 5% and 24% in mixtures made with 15% and 30% FAC, respectively.
On the other hand, the mortar using PFAC exhibited similar compressive
and flexural strengths compared to the control group. For the mortar
with 15% PFAC, the compressive strength was only 1.4% less than the
control group, and the flexural strength was approximately the same as
the control group. This clearly indicates that the use of 15% PFAC can
make up for the compressive and flexural strengths loss caused by the
inherent porosity and lower elastic modulus of the FAC. This is because
the IC water released in PFAC can prolong the hydration of cement-
based materials and promote strength of the LC3 mortar.
However, some studies have shown that the use of traditional IC
agents such as SAP and lightweight aggregate for IC cannot make up for
the strength loss caused by themselves [36,37]. For example, when 0.3%
addition of SAP is added, the compressive strength of concrete decreased
by about 10% at 28 days [22]. As an IC agent, the higher strength caused
by PFAC is also related to its morphological characteristics. The spher­
ical shape of PFAC can minimize the stress concentration from pores.
However, the compressive and flexural strengths of mortar are still
lower than that of control group when the dosage increased to 30%.
Chen et al. [23] shows similar trend, that the addition of FAC and PFAC
can decrease the strengths. It means that at this dosage of PFAC (30%),
the effect of IC on strengthening cannot compensate for the strength loss
caused by FAC/PFAC.
4.5. Effect of internal curing on kinetic of hydration products
The IC agent used in this study is essentially fly ash with pozzolanic
activity, and its replacement of quartz sand may change hydration de­
gree. Result of autogenous shrinkage showed that PFAC with IC water
can improve the autogenous shrinkage resistance of mortars. However,
whether the pozzolanic activity of FAC improves the early hydration of
the material, or the additional IC water compensate for the rapid loss of
water including that between successive layers in 3D printing needs
further study. In order to clarify the influencing mechanism of PFAC on
pozzolanic activities of mortars, XRD analysis of the mortar made with
and without the FAC/PFAC was carried out at different ages, and the
diffraction patterns were shown in Fig. 12.
It can be seen from Fig. 12 that mortars made with FAC/PFAC
showed similar X-ray diffractogram patterns as those of the control
J.-L. Tao et al. Construction and Building Materials 346 (2022) 128247

(a) (b)

29.0 29.5 30.0 29.0 29.5 30.0

2 (°) 2 (°)

10 15 20 25 30 35 40 45 50

Fig. 12. X-ray diffractogram patterns of mixtures at (a) 1 and (b) 28 days.

(a) (b)
0.2
1d 0.2 28d
0.0 0.0

-0.2 -0.2

-0.4
-0.4
-0.6
-0.6
-0.8

-0.8 -1.0

-1.2
-1.0
-1.4
-1.2
-1.6

-1.4 -1.8
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature ( ) Temperature ( )
Fig. 13. DTG curve of mixtures at (a) 1 and (b) 28 days.

group, which were calcium hydroxide (CH), calcium silicate hydrate (C-
S-H), hemicarbaluminate (Hc) and monocarbonate (Mc) at 1 and 28
days. As the days increases, the samples containing FAC/PFAC show the
same trend as the control sample. The peak of all samples corresponding
to Mc were gradually obvious, while the peak of Hc presented a trend of
increasing first and then decreasing from 1 to 28 days. This phenomenon
was consistency with the hydration process of LC3 in literatures[38,39].
It indicates that there were no new hydration products produced when
the FAC/PFAC were added. Rheinheimer et al.[40] reported that the
pozzolanicity of FAC was not high at room temperature. However, by
comparing the change of the corresponding peak value (29.4◦ ) of C-S-H/
calcium carbonate (Cc), it can be found that the sample containing 30%
PFAC presented the strongest peak, and the strength of the peak
decreased from 1 to 28 days. However, the incorporation of FAC without
IC water did not present this phenomenon. Since the content of lime­
stone in different mixtures was the same, it can be inferred that the
change of the peak value was mainly due to the content of C-S-H. This
indicates that the addition of PFAC can promote the formation of C-S-H
in the early stage of the composites, and the influence was gradually
increased with the increase of PFAC content. This may be because a large
amount of silica in the PFAC can promote the generation of early C-S-H,
and PFAC with extra IC water can indeed supply sufficient water for
hydration [41].
The above XRD experimental phenomenon can be confirmed by TG
analysis, as shown in Fig. 13. It can be seen that the mass loss between
100◦ and 150◦ of the component containing PFAC is greater at the age of
1 day compared with samples made with and without FAC. This phe­
nomenon confirms the conclusion of XRD pattern that PFAC can pro­
mote the formation of C-S-H. However, the samples containing FAC or
PFAC had an insignificant peak in the range of 150◦ to 200◦ compared
with the control sample made without FAC. Based on the above dis­
cussion, it can be speculated that the change of this peak can be
attributed to the difference generated content of in Hc and Mc. Thus,
although FAC/PFAC introduce more alumina, it still cannot promote the
formation of early carbonaluminate. This may be due to the fact that the
moisture loss of the sample is not significant under standard curing
conditions (temperature 20 ± 5 ◦ C, humidity 95%). At this time, the
effect of IC is not obvious.
The DTG chart of the 28-day samples showed that samples contain­
ing FAC/PFAC have a greater mass loss in the range of 150◦ to 200◦ than
the control groups. This indicates that the samples in the later hydration
stage had more Hc and Mc under standard curing conditions, showing a
more obvious IC effect. Therefore, under standard curing conditions, the
influence of IC on hydration mainly occurred in the later stage. At 28

9
J.-L. Tao et al.
Fig. 14. Microstructure investigation of PFAC particles in LC3 mortars cured for four ages: (a-b) 3; (c-b) 7; and (d-e) 14 days.
days, the LC3-PFAC15% mixture showed smaller mass loss between
100◦ and 150◦ compared to the control group. This may be due to the
high alumina content in PFAC and sufficient water, which increased the
aluminate concentration in the system and promoted the conversion of
ettringite to monosulfur-hydrated calcium sulfoaluminate (Ms). This can
also explain the increased mass loss of samples in the range of 150◦ to
200◦ .
In addition, the increased mass loss of samples containing PFAC in
10
Construction and Building Materials 346 (2022) 128247
the range of 150◦ to 200◦ may be attributed to the secondary hydration
reaction in the mortar, which consumes more CH and generates Hc and
Mc. When the IC effect works, the water loss in the system is slower,
which ensures the processing of hydration reaction. Meanwhile, the 28-
day samples with PFAC show more mass loss between 700◦ and 800◦ ,
which corresponds to the content of calcium carbonate. This phenom­
enon can be explained by the addition of FAC/PFAC, which allows more
alumina to react with calcium carbonate, resulting in more carbon
J.-L. Tao et al.
aluminate production.
4.6. Microstructural analysis
The microstructure of the LC3 composites containing PFAC at 3, 7,
and 14 days was characterized by environmental scanning electron
microscopy, as shown in Fig. 14.
As shown in Fig. 14(a), the PFAC are randomly distributed in the
mortar, indicating that they are well dispersed in the LC3 composites.
Moreover, it can be observed that most of the PFAC are intact and un­
broken state, indicating that the strength of the thin wall of PFAC in the
early hydration stage is still higher than that of the LC3 matrix, and it
maintains a good bond with LC3 matrix. In addition, some C-S-H gel was
formed on the surface of PFAC in the early hydration stage. This is
related to the pozzolanic activity of the PFAC [42]. Fig. 14(b) shows the
internal structure of different size PFAC after crushing. It can be seen
that some hydration products have been generated inside PFAC, while
some of the PFAC have a clear interior. According to the above discus­
sion of hydration products, the pozzolanic activity of PFAC at early age
is low, so the hydration products inside PFAC may be due to the ingress
of fine particles from matrix. This depends on the size of the puncture
hole on the surface of the PFAC. Most of the PFAC particles that have
produced hydration product inside have larger penetration holes.
Fig. 14(c and d) show that some hexagonal AFm and cluster C-S-H gel
are produced inside the PFAC, which indicates that the PFAC may
participate in the hydration reaction at 7 days. Furthermore, non-
penetrating cracks were observed around the PFAC. Although PFAC
and LC3 matrix have a good interface bonding, the interfacial transition
zone can still be weak. Additionally, in Fig. 14(d), some penetrating
holes on the surface of the PFAC were filled with hydration products,
which may hinder the penetration of IC water. The weak interface and
the hinder of penetration can be also responsible for the strength decline
of mortars caused by the use of PFAC at 7 days.
In Fig. 14(e and f), the wall of some PFAC is shown to be almost
consumed, and a large amount of rod-like ettringite is generated after
14 days of hydration. Fig. 14(f) can also confirm that a large number of
hydration products are produced on the surface of most of the observed
PFAC particles. At this point, PFAC is basically integrated with the hy­
drated cement matrix.
5. Conclusion
This study attempts to develop a novel printable LC3 composite
containing IC agent to alleviate the risk of autogenous shrinkage in 3D
printing materials. Perforated fly ash cenosphere was used as an IC agent
to improve the autogenous shrinkage resistance and interlayer bonding
of the 3D printed components. Moreover, a novel FBG technology was
proposed to monitor the autogenous shrinkage of 3D printed samples to
evaluate the IC effect of PFAC. Mechanical strength was also employed
to determine the effect of IC on the performance of the LC3 composites.
Additionally, microstructure and the hydration products were analyzed
through SEM, XRD, and TG tests to investigate the mechanism of action
of the PFAC. Based on the results of this study, the following conclusions
can be made:
1. Rheological properties of LC3 mortar made with 15 vol% FAC were
similar with that of the control group and increased significantly
when the FAC content increase to 30 vol%. This can be due to the
“ball-bearings” effect and great packing density of the binder mate­
rial. However, mortar mixtures containing PFAC had lower rheo­
logical properties than the mortar with FAC, which can be due to the
releases of water outward under the action of shear stress, thus
increasing the lubrication between the cementitious particles.
2. Autogenous shrinkage strain of mortar containing 15 vol% PFAC was
81% lower than that of mortar without PFAC, indicating that IC ef­
fect contributed by PFAC can effectively reduce the autogenous
11
Construction and Building Materials 346 (2022) 128247
shrinkage of the LC3 composite material. Furthermore, the addition
of PFAC can effectively maintain the moisture at the interlayer of the
3D printed components, thus enhancing the interlayer bonding of the
samples.
3. Mechanical properties of LC3 mortar can be reduced when using the
FAC to replace fine aggregate due to the hollow morphology and low
strength and elastic modulus of the FAC. However, the incorporation
of PFAC as an IC agent in LC3 mortar can effectively make up for the
strength loss. The optimal sand replacement content of the PFAC was
15 vol%.
CRediT authorship contribution statement
Jie-Lin Tao: Investigation, Writing – original draft. Can Lin: Data
curation, Writing – review & editing. Qi-Ling Luo: . Wu-Jian Long:
Methodology, Writing – review & editing. Shu-Yi Zheng: Data curation.
Chen-Yu Hong: Visualization.
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.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work was supported by the National Natural Science Founda­
tions of China, NSFC-Shandong Joint Fund (No. U2006223), and the
Science and Technology Project of Shenzhen, China (No.
JCYJ20190808151011502, No. JCYJ20180305124844894).
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