Construction and Building Materials 212 (2019) 192–201

Contents lists available at ScienceDirect

Construction and Building Materials

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

Effect of retarders on the early hydration and mechanical properties

of reactivated cementitious material
Linglei Zhang a,b,c, Yongsheng Ji a,b,c,⇑, Jun Li c, Furong Gao c, Guodong Huang c
a
Jiangsu Key Laboratory of Environmental Impact and Structural Safety in Engineering, China University of Mining and Technology, Xuzhou, Jiangsu 221008, China
b
State Key Laboratory for Geomechanics and Deep Underground Engineering, School of Mechanics & Civil Engineering, China University of Mining and Technology, Xuzhou,
Jiangsu 221008, China
c
Jiangsu Collaborative Innovation Center for Building Energy Saving and Construction Technology, Xuzhou, Jiangsu 221116, China

h i g h l i g h t s

 The retarding effects of different retarders on DCRCM are variable.

 Borax can effectively reduce initial hydration rate and increase setting time.
 The best mechanics properties can be obtained when borax amount is 2%.
 The mechanism for retarding effect of borax on DCRCM paste is analyzed.

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

Article history: Effects of different retarders (gypsum, sodium citrate, sodium gluconate and borax) on setting and hard-
Received 8 September 2018 ening behaviors of dehydrated cement paste (DCP) composite reactivated cementitious materials
Received in revised form 28 March 2019 (DCRCM) are studied through determinations of setting time and mechanical properties. Mechanism of
Accepted 29 March 2019
Early hydration and hardening is also studied based on hydration kinetics and SEM analysis. The results
indicate that sodium citrate and gypsum are of poor retarding effect on DCRCM. Proper amount of borax
will effectively retard the setting process. Sodium gluconate is of best retarding effect, whereas it will
Keywords:
result in low early strength of DCRCM. When used as a retarder, borax is of obvious retarding effect. It
Dehydrated cement paste
Retarder
can not only effectively restrain initial hydration process of DCRCM, but also accelerate early hardening
Borax process of DCRCM, promoting the establishment and development of mechanics strength. When the mix-
Setting time ing amount of borax is 2%, both early and late strengths of DCRCM can reach to the maximum. SEM anal-
Early hydration ysis shows that the hardening paste of DCRCM with borax is characterized by dense microstructure and
less defects, greatly improving the mechanical properties of DCRCM.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Recycled aggregate concrete can be used as a building material.
Therefore, it is of great environmental value, and lots of researches
have been done on it by researchers at home and abroad during
recent years, obtaining plenty of research achievements [1–4].
However, Fine powders less than 0.15 mm, mainly consisting of
hardened cement paste (HCP), are produced during the preparation
process of recycled aggregate concrete by using waste concrete. An
effective way of reusing waste concrete is gelling property recy-
⇑ Corresponding author at: Jiangsu Key Laboratory of Environmental Impact and
Structural Safety in Engineering, China University of Mining and Technology,
Xuzhou, Jiangsu 221008, China.
E-mail address: jyscumt@sina.com (Y. Ji).
cling of these fine powders, which has been a major concern of
waste concrete reutilization [5–7].
Researches show that dehydrated cement paste (DCP), obtained
from HCP with high temperature calcination, has partially recov-
ered cementitious capacity [8–11]. In our previous research [12],
DCP can be modified with GGBFS based on micro-ball milling effect
and micro-aggregate effect, producing DCP composite cementi-
tious material (DCRCM) with excellent properties. But when the
DCRCM is used as a cementitious material, there are still some
inevitable problems such as short setting time and quick fluidity
loss, which will not meet construction requirements in practical
engineering. Therefore, the retarder research of DCRCM is the key
to cementitious property recycling of waste concrete.
Suitable amount of gypsum is added to solve fast setting prob-
lem of Portland cement. The dissolution rate of gypsum is higher

https://doi.org/10.1016/j.conbuildmat.2019.03.323
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201
than hydration rate of C3A in cement clinker, and thus the hydra-
tion product of C3A, i.e. C4AH13, will immediately react with dis-
solved gypsum to form ettringite, which prevents fast setting due
to the formation of network structure from the lamellar crystal
of C4AH13 [13]. And it is the basic reason that gypsum is of retard-
ing ability when added to Portland cement. Compared with Port-
land cement, the microstructure of DCP powders with high
specific surface area is loose and porous [14,15]. DCP mainly con-
tains dehydrated phases of C-S-H, which is in metastable state
and hydrates fast [16]. Free calcium oxide, produced from dehydra-
tion of calcium hydroxide in HCP, will react with water instanta-
neously to produce large amounts of heat, thus further
quickening setting process of DCP. However, the dissolution rate
of gypsum, with low dissolubility, is obviously lower than the
hydration reaction rate of DCP, which is much higher than Ordi-
nary Portland cement (OPC) [7]. Therefore, gypsum can neither
promptly react with aluminate hydration product of DCP nor delay
hydrations of dehydrated phases of C-S-H and free calcium oxide.
As a result, gypsum cannot work as a retarder to solve the prob-
lems of fast setting when DCRCM is used in practice. Due to the
retarding effect of gypsum on C3A hydration, other common retar-
ders added to Portland cement, such as sodium gluconate [17,18]
and sodium citrate [19], mainly aim at crystallization ratios of both
C3S [20]and Ca(OH)2. Hence, whether these retarders will work for
DCRCM, which mainly consists of dehydrated phases of calcium
silicate hydrate, aluminate and Ca(OH)2, needs further study.
Borax, a weakly alkaline salt, is a kind of inorganic retarder [21],
and can easily dissolve in water. When dissolved in water, borax
can react with Ca2+ to form a calcium-base borate layer in alkaline
solution [22]. DCRCM paste is strong alkaline, of which PH value
can reach 12. When mixed with DCRCM, borax may be capable
of retarding effect due to the fast-produced complex, which may
retard hydration and crystal separation of the cementitious sys-
tem. Moreover, the solubility of borax is far larger than that of gyp-
sum, which makes it more advantageous in terms of retarding
effect. The setting process of DCRCM may be delayed in this way.
In this paper, the influences of gypsum, sodium citrate, sodium
gluconate and borax on setting time and compressive strength of
DCRCM are investigated to determine the optimum retarder with
well retarding effect and mechanical properties. Heat evolution
rate and hydration heat of DCRCM with different mixing amounts
of the optimum retarder are also studied. By hydration kinetics and
SEM analysis, mechanisms of early setting and hardening process
of DCRCM are analyzed.
2. Materials and methodology
2.1. Materials
Ordinary Portland cement (OPC) was provided by China United Cement Co., Ltd,
with the characteristics presented in Table 1. The Blaine surface areas was 350 m2/
kg.
Table 1
Chemical composition of OPC, GGBFS and DCP.
Materials OPC GGBFS
SiO2 24.55 36.51
Al2O3 7.77 15.65
Fe2O3 3.62 1.08
CaO 54.59 32.93
MgO 2.68 8.02
Na2O 0.31 0.81
K2O 1.5 1.11
SO3 2.24 0.07
L.O. I 1.2 1.33
193
In accordance with the results of a previous study, DCRCM can be obtained by
grinding the mixtures of DCP and ground granulated blast-furnace slag (GGBFS) at
the mass ratios of 2:1. The detailed procedures of DCRCM preparation are shown in
Reference [12]. The chemical compositions of GGBFS and DCP were presented in
Tables 1.
Chemical grade powders of gypsum (G), sodium citrate (SC), sodium gluconate
(SG) and borax (B) with the purity higher than 99% were adopted in the paste for-
mulation. The superplasticizer used here was polycarboxylic acid type with a solid
mass fraction of 25%.
2.2. Methodology
2.2.1. Water requirement of normal consistency and setting time
Referring to the State Standard of China (GB/T1346-2011), measurement of
water requirement of normal consistency and setting time of DCRCM with different
retards (sodium citrate, borax, sodium gluconate and gypsum) were determined to
investigate the influence of different retarders on water requirement of normal con-
sistency and setting time of DCRCM. Sodium citrate, borax, and sodium gluconate
were respectively tested with both amounts of 2% and 4% by mass of DCRCM,
and gypsum was tested with both amounts of 4% and 8%. The paste of pure DCRCM
without any retarders was used as the control sample. All retarders should be pre-
dissolved in the mixing water to assure homogeneous distribution of the retarders
in the samples, and then mixed with DCRCM.
The dosages were chosen to clearly distinguish the effects of retarders on set-
ting time and compressive strength. However, the effects of retarders might change
with dosage variation, which were not investigated in this paper.
2.2.2. Compressive strength
All DCRCM mortars were mixed with water-to-binder ratio of 0.5 (the mixture
proportions of binders are same to the above 1.2.1 section), and binder-to-sand
ratio of 1:3. Then DCRCM mortars were casted into 40 mm  40 mm  160 mm
molds to determine the compressive strength in accordance with the specifications
of the State Standard of China (GB/T17671-1999). The OPC mortar was also pre-
pared with the same conditions of DCRCM mortars. Specimens were consolidated
using a vibrating table and trowel finished. Cast specimens were stored in a moist
curing room with humidity of more than 95% RH and temperature of 20 ± 2 °C.
Compressive strength was determined using a hydraulic compression tester at
3 days and 28 days.
2.2.3. Hydration kinetics
Referring to the State Standard of China (GB/T12959-2008), measurement of
heat evolution rate and hydration heat of DCRCM were determined by a semi-
adiabatic calorimeter to investigate the influence of borax amounts (0%, 1%, 1.5%,
2%, 4%) on the hydration kinetics of DCRCM. All measurements lasted for 3 days.
All samples were mixed with water-to-binder ratio of 0.5 and binder-to-sand
ratio of 1:3, separately. Each sample contained 450 g DCRCM, 1350 g standard sand
(ISO) and 225 g water (with superplasticizer and borax). After fully mixed, the
mixer was quickly taken down, and the mortar was mixed by a spoon for several
times. Then two mortar samples of (800 ± 1) g were weighted by electronic balance
and packed into the measuring container, respectively.
2.2.4. Scanning electron microscopy
SEM analysis was performed on the samples of both pure DCRCM and DCRCM
with 2% borax (water-binder-ratio 0.5) at hydration time of 3 days and 28 days.
The fresh surfaces from the representative samples, without polishing to keep the
fractured surface uncontaminated, were used for SEM analysis to investigate the
microstructure development of the specimens. The SEM analysis was performed
in low vacuum mode using the FEI Quanta 250 with an accelerating voltage of
15 kV.
3. Results and discussions
3.1. Water requirement of normal consistency
Water requirements of normal consistency of DCRCM with dif-
ferent admixtures are shown in Fig. 1. As shown in Fig. 1, water
DCP requirement of normal consistency of pure DCRCM is 0.6. And
30.26 water requirements of normal consistency of DCRCM, respectively
6.64 with 4% gypsum, 1% sodium citrate, 1% sodium gluconate and 1%
2.54 borax, are 0.55, 0.57, 0.53 and 0.42. Compared with pure DCRCM,
46.47
2.42
water requirements of normal consistency of DCRCM with differ-
0.7 ent admixtures are with varying decrease. The more retarders are
1.63 added, the more water requirement of normal consistency
2.25 decreases. Among the retarders, sodium citrate is of the poorest
4.97
effect. Even if the amount of sodium citrate increases to 2%, there
194 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201

Borax, as a retarder, shows better retarding effect. When borax

amount is 1%, initial setting time and final setting time of DCRCM
are 45 min and 78 min respectively. And when borax amount
increases to 2%, initial setting time and final setting time of DCRCM
prolong to 85 min and 125 min respectively, much higher than
those of pure DCRCM. Therefore, the setting time of DCRCM with
borax is greatly prolonged. When the amount of sodium gluconate
is 1%, the initial setting time and final setting time of DCRCM are
90 min and 155 min respectively. And the initial setting time and
final setting time respectively reach to 125 min and 205 min in
the paste of DCRCM with 2% sodium gluconate. The setting time
of DCRCM with sodium gluconate greatly increases and its retard-
ing performance is significantly better than any other retarders.
In conclusion, the retarding effects of sodium gluconate, borax,
sodium citrate and gypsum tend to be worse gradually. Whereas,
all of the retarders can prolong setting time of DCRCM to some
degree, which provides basic conditions for the investigation of
hydration and hardening properties of DCRCM.
Fig. 1. Water requirement of normal consistency.

is no obvious decrease in water requirement of normal consistency 3.3. Compressive strength

of DCRCM.
When the borax amount is 2%, water requirement of normal Compressive strengths of DCRCM with different retarders are
consistency of DCRCM decreases to 0.45. For sodium gluconate, shown in Fig. 3. It can be obtained from Fig. 3(a), the 3 days com-
when its mixing amount is 2%, water requirement of normal con- pressive strengths of OPC and pure DCRCM are 27.6 MPa and
sistency of DCRCM is 0.35, reducing 41.7% compared with that of
DCRCM without any retarders. In conclusion, the influences of
sodium citrate, gypsum, borax, and sodium gluconate on water
requirement of normal consistency of DCRCM tend to be gradually
greater.

3.2. Setting time

Setting times of DCRCM with different retarders based on the

water requirement are shown in Fig. 2. As is shown in Fig. 2, the
initial setting time and final setting time of pure DCRCM are
23 min and 45 min respectively. The initial setting time and final
setting time of DCRCM with 4% gypsum are 25 min and 48 min
respectively. When gypsum amount reaches to 8%, initial setting
time only increases to 42 min. Therefore, gypsum has little influ-
ence on setting time of DCRCM, which indicates that gypsum is
barely capable of retarding when added to DCRCM. When sodium
citrate amount is 2%, the initial setting time and final setting time
of DCRCM are 40 min and 73 min respectively. Setting time of
DCRCM with sodium citrate is remarkably increased compared
with that of pure DCRCM, but its setting rate is still quite fast.

Fig. 3. Effect of retarders on the compressive strength of DCRCM: (a) 3 days; (b)
Fig. 2. Effect of retarders on the setting time of DCRCM. 28 days.
 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201
29.5 MPa respectively. The compressive strength of DCRCM with
4% gypsum is equivalent to that of pure DCRCM. When gypsum
amount reaches to 8%, the compressive strength decreases slightly
(25.6 MPa). While the compressive strength of DCRCM with 2%
sodium citrate significantly decreases to 5.6 MPa. Therefore,
sodium citrate shows negative effect on early strength develop-
ment of DCRCM. When the amount of borax is 1%, the compressive
strength of DCRCM is 31.4 MPa, slightly higher than that of pure
DCRCM. When the borax amount reaches to 2%, the compressive
strength of DCRCM reaches the maximum value of 37.4 MPa,
26.7% higher than that of pure DCRCM. Therefore, borax can greatly
promote early strength development of DCRCM. When sodium glu-
conate amount is 2%, the compressive strength of DCRCM is only
10.5 MPa, which results from strong retarding effect of sodium glu-
conate. Thus, the early hydration rate of DCRCM is quite low and
the setting process is excessively prolonged. As a result, the
amounts of hydration products decrease, which affects the early
strength development of DCRCM.
The 28 days compressive strength variations of DCRCM with
different retarders are similar to 3 days compressive strength
(see Fig. 3(b)). The 28 days compressive strengths of DCRCM,
respectively mixed with gypsum and sodium citrate, are lower
than that of pure DCRCM. Moreover, the compressive strength
tends to decease more with increasing amounts of the two retar-
ders. When sodium gluconate amount is 1%, the compressive
strength (42.3 MPa) is slightly higher than that of DCRCM without
any retarders (40.5 MPa). The compressive strength of DCRCM
with 2% sodium gluconate is equivalent to that of pure DCRCM.
Compared with 3-day compressive strength of DCRCM with
sodium gluconate, it can be obtained that although sodium glu-
conate has strong retarding effect on the setting process of DCRCM,
leading to lower early strength, it has no negative influence on the
development of latter strength. The highest 28 days compressive
strength can be obtained when the borax amount is 2%
(53.2 MPa), which is 34.3% higher than that of pure DCRCM and
8.8% higher than that of OPC (48.9 MPa). Therefore, borax has good
promoting effect on later strength of DCRCM.
In conclusion, the retarding effects of gypsum and sodium citrate
are quite poor. Moreover, the compressive strengths of DCRCM,
respectively mixed with gypsum and sodium citrate, decease to
some degree. Sodium gluconate shows the best retarding ability,
while it has negative influence on the early strength development.
Although the latter strength of DCRCM with sodium gluconate is
improved compared with its early strength, the strength increase-
ment is not obvious compared with that of pure DCRCM. Borax exhi-
bits obvious retarding effect and the mechanical property of DCRCM
can be significantly improved at both early and later stage. There-
fore, borax is used as the retarder for DCRCM, and the mechanisms
of its influence on setting and hardening process are studied.
3.4. Hydration kinetics
3.4.1. Exothermic rate
Exothermic rate curves of OPC and DCRCM are illustrated in
Fig. 4. As shown in Fig. 4, OPC strongly reacts with water when
they are mixed together, and the exothermic rate is quite fast
due to dissolution of cement minerals and quick hydration of
C3A, corresponding to the pre-induction period. Then the hydration
progress of OPC enters the induction period, during which period
the exothermic rate quickly decreases to a low value for 1–2 h.
Whereafter, exothermic rate speeds up due to formation of large
amounts of C-S-H. This period is referred to as the acerbation per-
iod. Then exothermic rate gradually decreases and enters the
steady period.
The hydration reaction of pure DCRCM is much violent than
OPC, the initial exothermic rate is almost 5 times than OPC and
195
Fig. 4. Effect of borax amounts on the hydration exothermic rate of DCRCM.
lasts for approximately 30 min. Hydration exothermic rate declines
obviously with increasing borax amounts during this period, which
indicates that initial hydration process (hydration time 30 min)
can be effectively retarded by borax.
After the violent reaction, the exothermic rate of pure DCRCM
becomes lower. This period is known as the induction period. How-
ever, time for induction period of pure DCRCM is delayed com-
pared with that of OPC. The induction period lasts for 5–6 h, and
this period appears to be shorter with increasing borax amounts.
When the borax amount is 2%, there is nearly no induction period.
The above results illustrate that apart from obvious setting retard-
ing effect of initial setting, borax can also promote harden process
of DCRCM, and the promoting effect is evident with increasing
borax amounts. However, when borax amount is 4%, the induction
period trend to be longer, which indicates that excessive amounts
of borax will result in over setting of DCRCM.
After induction period, the exothermic rate of DCRCM speeds up
again and the main exothermic rate peak occurs, known as the
acceleration period. The main exothermic rate peak of DCRCM will
gradually increase with increasing borax amounts, which further
indicates that borax can promote hardening process of DCRCM
after initial setting. However, the exothermic peak of DCRCM with
4% borax is obviously lower than that of DCRCM with other borax
amounts in acceleration period, which is due to the influence of
excessive borax amount on hydration process of DCRCM.
From the above results, it can be obtained that with increasing
borax amounts, the exothermic rate significantly decreases in the
preinduction period, and that the induction period will be signifi-
cantly shortened, which greatly promotes the hydration process
of DCRCM after initial setting [23]. However, excessive borax
amount will result in longer induction period and lower exother-
mic rate, and thus the hydration process of cementitious system
is severely restrained, which is disadvantageous for the establish-
ment and development of early strength.
3.4.2. Hydration heat
Hydration heat curves of OPC and DCRCM are shown in Fig. 5.
As shown in Fig. 5, in early hydration stage (usually hydrated for
3 days), hydration heat of pure DCRCM and OPC is 276.0 J/g and
163.4 J/g, respectively. When the amount of borax increases from
1% to 2%, hydration heat of DCRCM increases from 303.1 J/g to
385.5 J/g, which increases 39.67% compared with that of pure
DCRCM. This further demonstrates that borax can promote early
196 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201
Fig. 5. Effect of borax amounts on the hydration heat of DCRCM.
hydration process of DCRCM. When the borax amount is 4%, the
setting time of DCRCM will be prolonged, and hydration exother-
mic rate will be lower, thus resulting in decreasing hydration heat.
In conclusion, borax is capable of restraining initial hydration
(hydration time 30 min) and promoting early hydration (usually
hydrated for 3 days). Therefore, initial hydration rate can be
declined and the setting time of DCRCM can be prolonged, and thus
the objective of retarding is achieved. Moreover, borax can also
improve the early strength due to promoting effect of early hydra-
tion of DCRCM. Therefore, borax is a suitable retarder for DCRCM.
3.5. Scanning electron microscopy
Fig. 6 shows the microstructure of DCRCM pastes with different
amounts of borax at 3 days. As is shown in Fig. 6 (a), bonding
among hydration products of DCRCM without borax is not tight,
and the bonding strength among the hydration products of DCP
and GGBFS particles is quite low. Obvious cracks and pores exist
at the interfacial zones among hydration products of DCP and
GGBFS particles (GGBFS particles are regarded as micro-
aggregate due to relatively weak activity), resulting in relatively
loose microstructures and further low mechanical properties.
Hydration action of DCP without any retarders can take place
quickly to form a large amount of gels in a short time, but the
hydration products mainly consist of coarse and complete crystal-
lization like Ca(OH)2, resulting in loose microstructure and poor
bonding strength. Therefore, lots of perfect crystalline hydration
products and quite a lot of defects exist in the hydration products
of DCP, which contributes little to the bonding strength and
mechanical property (see Fig. 6 (b)).
Fig. 6 (d) and Fig. 6 (e) show the microstructure of DCRCM with
2% borax at 3 days. As is shown in the Fig. 6 (d), interwoven gel
particles form the network structure of network gel, of which the
flocculation gel accounts for a considerable amount. The gel then
interconnects with each other to form integrated structures.
Hydration products of DCP can bond well with GGBFS particles,
and therefore compact structures and reliably tight bonding can
be formed at the interfacial zone (Fig. 6 (e)). Moreover, there is
no large porous structures inside the hardened paste of DCRCM,
and no perfect crystalline hydration products are found, meaning
that the whole structure is compact. The above analyses illustrate
that DCP can fully react with GGBFS particles. Meanwhile, apart
from good retarding ability, borax can significantly promote estab-
lishment and development of mechanics properties for the whole
cementitious system, which greatly increases hydration degree of
cementitious system.
At the hydration of 28 days, the hydration products amount of
DCRCM without borax will increase with the increase of hydration
degree (see Fig. 7(a)), and the bonding between DCP and GGBFS is
enhanced. Moreover, good bonding has been formed at the interfa-
cial zones. Large porous structures will be smaller and smaller due
to filling of hydration products and thus density is improved (see
Fig. 7(b)). However, there still exist some defects inside the hard-
ened paste. Therefore, whole performances of DCRCM tend to be
poor. With the amount of hydration products gradually increasing,
compactness of hardened paste of DCRCM with 2% borax has been
further improved (see Fig. 7(d)). Therefore, the bonding becomes
much tighter among the hydration products of DCP and GGBFS par-
ticles, and barely no single GGBFS particles can be found (see Fig. 7
(e)), which have been encapsulated by the hydration products of
DCP. Thus, the bond strength among the interfacial zones are fir-
mer, resulting in good whole performances.
The chemical compositions of the hydration products are mea-
sured by an EDS test based on the obtained SEM images. The
results of element mapping of Fig. 6(b), (d) and Fig. 7(c), (e) are
shown in Fig. 6(c), (f) and Fig. 7(c), (f), which corresponds to pure
DCRCM and DCRCM-2%B paste at 3 days and 28 days of age. The
results of EDS elemental mapping show that the major elements
of hydration products of the DCRCM pastes are calcium, silicon,
aluminum and magnesium, which mainly attributes to the formed
C-S-H gel, Ca(OH)2 and unhydrated particles of DCP and GGBFS in
the pastes.
4. Mechanism analysis
4.1. Quick setting analysis of DCRCM
Cementitious properties of DCRCM are mainly dependent on
activities of DCP, and GGBFS is more used as supplementary
cementitious materials [24,25]. Therefore, physical, chemical prop-
erties and cementitious properties of DCRCM are largely depen-
dent on properties of DCP. The essence of the preparation and
usage process of cementitious materials lies in the change process
of SiO4 tetrahedron from the polymerization state to the isolated
state and then to the polymerization state. While material activa-
tion is the depolymerization process of polymeric SiO4 tetrahe-
dron. The preparation process of DCP is a thermal activation
process. During this process, the main hydration productions of
HCP will dehydrate: ettringite, low sulphated calcium sulfate and
calcium hydroxide will decompose, losing combined water to pro-
duce dehydrated phases of aluminate, C12A7, and calcium oxide.
For C-S-H gel, it will not only dehydrate but also depolymerize,
changing into a low polymerization state [26–28].
Generally, the lower polymerization degree of the network
structure is, the higher hydraulic activity will be. Therefore, DCP
is of high activity. Both dehydrated phases of C12A7 and C-S-H exist
in the metastable state; and calcium hydroxide will dehydrate to
produce large amounts of f-CaO. As a result, DCP will quickly rehy-
drate when mixed with water. Moreover, DCP is loose and
porous [14,15], resulting in hydration reaction taking place at both
sides around the original boundaries of the particles at the same
time (see Fig. 8) [12], which greatly increases actual reaction area
of hydration. Hence, problem of fast setting exists for DCRCM
application, which in return increases the difficulty in fully
utilizing it.
4.2. Retarding analysis
4.2.1. Hydration process of DCRCM without retarder
Based on the results obtained from the above analysis, the
mechanism of borax effect on the setting process of the DCRCM
 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201 197

Fig. 6. SEM micrographs comparison of the samples at 3 days of age: (a), (b) pure DCRCM, (c) EDS result of pure DCRCM; (d), (e) DCRCM + 2%B, (f) EDS result of DCRCM + 2%B.

paste is illustrated in Fig. 9. DCRCM without any retarders reacts (I) Hydration of C-S-H in oligomer state. The hydration of C-S-H
with water quickly (see Fig. 9(a)). The main rehydration reaction in oligomer state mainly includes two parts. The first one is
contains three parts: water molecule and Ca2+ easily entering the original position
198 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201

Fig. 7. SEM micrographs comparison of the samples at 28 days of age: (a), (b) pure DCRCM, (c) EDS result of pure DCRCM; (d), (e) DCRCM + 2%B, (f) EDS result of DCRCM + 2%
B.

of the C-S-H dehydration phase to restore the C-S-H gel
structure and the dehydration phase polymerizing with each
other, which keeps the structure of C-S-H gel unchanged.
The other one is the hydration reaction of b-C2S produced
by C-S-H dehydration. Moreover, the C-S-H dehydrated
phase in the metastable state reduces the nucleation
barrier of C-S-H gel in the new cementitious system
and accelerates the formation of hydration products. There-
fore, the hydration rate of C-S-H dehydrated phase is very
fast.
 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201 199

Fig. 8. Hydration process of DCP particle.

Fig. 9. Control mechanism of borax on the setting process of DCRCM.

(II) Hydration of calcium oxide. The f-CaO reacts with water
quickly to reproduce calcium hydroxide, together releasing
large amounts of hydration heat, which can increase heat
exothermic rate of the whole cementitious system and make
the fresh paste lose its fluidity and set rapidly.
(III) Hydration of dehydrated Aluminate phases. The dehydrated
Aluminate phases are mainly C12A7. The coordination of Ca
and Al in the crystals is extremely irregular, and thus lots
of cavities exist in the structure. Water can easily get into
these cavities, which results in quick hydration and setting.
In the alkaline condition, C2AH8 with hexagonal structures
is quickly formed due to DCRCM hydration [29]. C2AH8 can
form network lapping, leading to fast setting of the fresh
paste. On the other hand, C12A7 are in metastable state and
DCP particles are loose and porous, thus leading to high heat
exothermic rate and large hydration area. Therefore, even if
200 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201
gypsum is added as a retarder, it cannot promptly react with
C2AH8 produced by hydration of C12A7 due to its low dissol-
ubility and dissolution rate. As a result, gypsum has limit
retarding ability for the cementitious system.
With the hydration reaction continuing, migration and diffusion
of the internal hydration products in the system are blocked, and
the internal hydration products accumulates in the inner of parti-
cles or among a few particles, causing the formation of flocculated
structure (see Fig. 9 (b)). The increasing of flocculated structure
will result in crystallization of hydration products, and the hydra-
tion product crystal is coarse (see Fig. 6 (b).). At the same time, the
amount of external hydration products is relatively reduced.
Therefore, no effective connections can be formed between the
external hydration products and particles outside, resulting in
more pores and poor integrity in the cementing system (see
Fig. 6 (a).).
4.2.2. Borax retarding analysist
4.2.2.1. Restrain formation of hydration production. As a retarder,
borax hydrolyzes to generate more borate ions in water before
mixed with DCRCM. Borate ions can react with Ca2+, hydrolyzed
production of DCRCM, and aluminate in dehydrated phases to form
a complex. The complex is similar to ettringite and its chemical for-
mula is 3CaO.Al2O3
3Ca(BO2)2
31H2O [30]. The complex will form a
thick film layer around the surfaces of DCRCM particles (see Fig. 9
(c)) [22,31–33], and it can effectively prevent water from entering
inside the DCRCM particles compared with common hydration
productions. So, water can barely penetrate inside the DCRCM par-
ticles, thus significantly restraining the hydration and crystalliza-
tion of DCRCM. Moreover, the formation of the film layer can
effectively consume C12A7 in dehydrated phases, preventing it
from hydrating to produce C2AH8. Meanwhile, hydration reaction
of DCRCM will only take place outside the original boundaries of
the DCRCM particles. Therefore, hydration area and heat exother-
mic rate are great reduced.
Apart from the hydration reaction of generating the complex,
borate ions can also react with Ca2+ to form wrapping layers of cal-
cium borate (see Fig. 9(c)) [34]. Wrapping layer of calcium borate is
similar to gel. It has the property of semipermeable membrane, so
water molecules and smaller ions can slowly penetrate inside the
DCRCM particles through the wrapping layers. The wrapping layers
will further wrap DCRCM particles to restrain DCRCM hydration
and prolong setting time. Furthermore, if the amount of borax is
excessive, the retarding effect is significantly improved and hydra-
tion rate is greatly reduced. However, the setting time of the
cementitious system is too long, resulting in decreasing of hydra-
tion products, which makes the establishment and development
of early strength greatly restrained.
4.2.2.2. Restrain crystallization of Ca(OH)2. Ion composition and con-
centration of fresh DCRCM paste are changed when borax is added
as a retarder. According to Joisel electrolyte dissolubility theory,
when there are strong cations in the solution, such as Na+ and
K+, they will reduce dissolubility of other weaker cations, such as
Ca2+ [27]. Therefore, Na+, introduced by borax, will reduce Ca2+ dis-
solubility of DCRCM. Moreover, borate ions can react with Ca2+ in
the solution to produce complex and calcium borate. These all help
to restrain crystallization of Ca(OH)2. As a result, the amounts of Ca
(OH)2 produced by the hydration of free CaO is effectively reduced
at the initial hydration period of fresh DCRCM paste. Meanwhile,
hydration heat due to the formation of Ca(OH)2 is also reduced,
which effectively lowers the hydration temperature and heat
exothermic rate of the cementitious system. Therefore, with the
increase of borax amount, electrolyte concentration increases at
the initial hydration period of fresh DCRCM paste, and thus Ca2+
dissolubility and Ca(OH)2 crystallization will be further restrained.
In conclusion, borax can reduce formation rate of hydration
products and restrain the crystallization of Ca(OH)2 in the cemen-
titious system. Thus, the setting process is prolonged. With hydra-
tion reaction continuing, unstable complex and borate wrapping
layer will be destroyed, resulting in reacceleration of hydration
reaction (see Fig. 9 (d)). Based on hydration heat analysis and
mechanics strength results, borax can effectively promote the
establishment and development of early strength of the cementi-
tious system. Besides, it can greatly improve late strength as well.
Therefore, borax can be used as an efficient retarder for DCRCM.
5. Conclusions
A systematically experimental study has been designed in order
to investigate the effects of different retarders (gypsum, sodium
citrate, sodium gluconate and borax) on setting and hardening
behaviors of DCRCM. Conclusions can be drawn as follows:
1) The retarding effects of different retarder on DCRCM are
variable. Gypsum and sodium citrate have poor retarding
effect. Borax can effectively prolong setting process of
DCRCM. Sodium gluconate has the best retarding ability
but leads to lower early strength.
2) Retarding effect of borax is quite obvious. Borax can effec-
tively reduce initial hydration rate of DCRCM and increase
setting time. Meanwhile, borax can quicken the hardening
process of DCRCM, thus promoting establishment and devel-
opment of early strength. Besides, borax can contribute to
the increase of the late strength. The best mechanics proper-
ties of DCRCM can be obtained when borax amount is 2%.
3) Microstructure analysis suggests that the hydration prod-
ucts of DCP has bonded well with GGBFS particles. Compact
structures and reliably tight bonding have been formed at
the interfacial zone. With the increase of hydration ages,
the microstructure and bonding at the interfacial zone are
further enhanced. Moreover, the whole structure of hard-
ened DCRCM paste is extremely compact and with little
defects.
4) The mechanism for retarding effect of borax mainly lies in
two aspects. On the one hand, borate, from the borax
hydrolyzation, can react with Ca2+and aluminate in dehy-
drated phase, and generate complex film layer and borate
wrapping layer, which can prevent water from penetrating
inside the particles of the cementitious materials. Thus, the
hydration rate of DCRCM will decrease and the generation
of hydration products will be restrained. On the other hand,
the crystallization of Ca(OH)2 can be effectively restrained
due to variations of the initial ion concentration and forma-
tion of calcium borate, and thus the setting process of
DCRCM is prolonged.
Acknowledgements
The authors would like to express their appreciations to the Project
supported by ‘‘the Fundamental Research Funds for the Central
Universities (2018XKQYMS02). The research works belong to one
part of the projects which are financially supported by FRFCU.
Conflict of interest
The authors declare that they have no conflict of interest to this
work.
 L. Zhang et al. / Construction and Building Materials 212 (2019) 192–201
We declare that we have no financial and personal relationships
with other people or organizations that can inappropriately influ-
ence our work, and there is no commercial or associative interest
that represents a conflict of interest in connection with the work
submitted.
References
[1] M. Amario, C. Rangel, M. Pepe, R.D.T. Filho, Optimization of normal and high
strength recycled aggregate concrete mixtures by using packing model, Cem.
Concr. Compos. 84 (2017) 83–92.
[2] J.Z. Xiao, C.H. Wang, T. Ding, A. Akbarnezhad, A recycled aggregate concrete
high-rise building: Structural performance and embodied carbon footprint, J.
Cleaner Prod. 199 (2018) 868–881.
[3] S. Omary, E. Ghorbel, G. Wardeh, Relationships between recycled concrete
aggregates characteristics and recycled aggregates concretes properties,
Constr. Build. Mater. 108 (2016) 163–174.
[4] C.J. Shi, Y.K. Li, J.K. Zhang, W.G. Li, L.L. Chong, Z.B. Xie, Performance
enhancement of recycled concrete aggregate - A review, J. Cleaner Prod. 112
(2016) 466–472.
[5] L.N. Lv, Y.J. He, S.G. Hu, Binding materials of dehydrated phases of waste
hardened cement paste and pozzolanic admixture, J. Wuhan Univ. Technol. 24
(2009) 140–144.
[6] A. Bordy, A. Younsi, S. Aggoun, B. Fiorio, Cement substitution by a recycled
cement paste fine: Role of the residual anhydrous clinker, Constr. Build. Mater.
132 (2017) 1–8.
[7] R. Yu, Z.H. Shui, Efficient reuse of the recycled construction waste cementitious
materials, J. Cleaner Prod. 78 (2014) 202–207.
[8] S.K. Handoo, S. Agarwal, S.K. Agarwal, Physical–chemical, mineralogical, and
morphological characteristics of concrete exposed to elevated temperatures,
Cem. Concr. Res. 32 (2002) 1009–1018.
[9] C. Alonso, L. Fernandez, Dehydration and rehydration processes of cement
paste exposed to high temperature environments, J. Mater. Sci. 39 (2004)
3015–3024.
[10] G.M. Wang, C. Zhang, B. Zhang, Q. Li, Z.H. Shui, Study on the high-temperature
behavior and rehydration characteristics of hardened cement paste, Fire
Mater. 39 (2015) 741–750.
[11] R. Serpell, M. Lopez, Reactivated cementitious materials from hydrated cement
paste wastes, Cem. Concr. Compos. 39 (2013) 104–114.
[12] L.L. Zhang, Y.S. Ji, G.D. Huang, J. Li, Y.J. Hu, Modification and enhancement of
mechanical properties of dehydrated cement paste using ground granulated
blast-furnace slag, Constr. Build. Mater. 164 (2018) 525–534.
[13] H.F.W. Taylor, Cement chemistry, 2nd ed., Thomas Telford, London, UK, 1997,
pp. 218–221.
[14] Q. Zhang, G. Ye, E. Koender, Investigation of the structure of heated Portland
cement paste by using various techniques, Constr. Build. Mater. 38 (2013)
1040–1050.
[15] G.F. Peng, Z.S. Huang, Change in microstructure of hardened cement paste
subjected to elevated temperatures, Constr. Build. Mater. 22 (2008) 593–599.
[16] M. Vyšvařil, P. Bayer, M. Chromá, P. Rovnaníková, Physico-mechanical and
microstructural properties of rehydrated blended cement pastes, Constr. Build.
Mater. 54 (2014) 413–420.
201
[17] G. Zhang, G. Li, Y. Li, Effects of superplasticizers and retarders on the fluidity
and strength of sulphoaluminate cement, Constr. Build. Mater. 126 (2016) 44–
54.
[18] F.B. Zou, H.B. Tan, Y.L. Guo, Effect of sodium gluconate on dispersion of
polycarboxylate superplasticizer with different grafting density in side chain, J.
Ind. Eng. Chem. 55 (2017) 91–100.
[19] I.R.D. Oliveira, A.R. Studart, F.A.O. Valenzuela, V.C. Pandolfelli, Setting behavior
of ultra-low cement refractory castables in the presence of citrate and
polymethacrylate salts, J. Eur. Ceram. Soc. 23 (2003) 2225–2235.
[20] S.H. Ma, W.F. Li, S.B. Zhang, D.S. Ge, J. Yu, X.D. Shen, Influence of sodium
gluconate on the performance and hydration of Portland cement, Constr. Build.
Mater. 91 (2015) 138–144.
[21] Q. Sun, J. Li, J. Wang, Effect of borate concentration on solidification of
radioactive wastes by different cements, Nucl. Eng. Design 241 (2011) 4341–
4345.
[22] H.B. Tan, Y.L. Guo, F.B. Zou, S.W. Jian, B.G. Ma, Z.Z. Zhi, Effect of borax on
rheology of calcium sulphoaluminate cement paste in the presence of
polycarboxylate superplasticizer, Constr. Build. Mater. 139 (2017) 277–285.
[23] G.X. Li, J.J. Zhang, Z.P. Song, C. Shi, A. Zhang, Improvement of workability and
early strength of calcium sulphoaluminate cement at various temperature by
chemical admixtures, Constr. Build. Mater. 160 (2018) 427–439.
[24] E. Deir, B.S. Gebreziabiher, S. Peethamparan, Influence of starting material on
the early age hydration kinetics and the composition of binding gel in alkali
activated binder systems, Cem. Concr. Compos. 48 (2014) 108–117.
[25] E. Altan, S.T. Erdogan, Alkali activation of a slag at ambient and elevated
temperatures, Cem. Concr. Compos. 34 (2012) 131–139.
[26] G.Y. Pan, R.Q. Mao, H.L. Zhang, Research of dehydrated calcium
sulphoaluminate hydrates (AFm) and its hydration, J. Wuhan Univ. Technol.
19 (1997) 28–30 (In Chinese).
[27] G.F. Peng, S.Y.N. Chan, M. Anson, Chemical kinetics of C-S-H decomposition in
hardened cement paste subjected to elevated temperatures up to 800 °C, Adv.
Cem. Res. 13 (2001) 47–52.
[28] L.N. Lv, Y.J. He, S.G. Hu, Structural characteristics of dehydrated phase of
hardened cement paste and its rehydrating ability, J. Chin. Ceram. Soc. 36
(2008) (2008) 1343–1347.
[29] W. Kurdowski, Cement and Concrete Chemistry, Springer, Netherlands, 2014,
pp. 607–611.
[30] M. Tong, X.G. Li, Concrete Admixture and its Application, China Architecture
and Building Press, Beijing, 2014, pp. 110–112 (In Chinese).
[31] S.L. Guo, H.J. Liu, Y. Shan, Y.H. Bu, The application of a combination of treated
AMPS/IA copolymer and borax as the retarder of calcium aluminate phosphate
cement, Constr. Build. Mater. 142 (2017) 51–58.
[32] D.A. Hall, R. Stevens, B. El-Jazairi, The effect of retarders on the microstructure
and mechanical properties of magnesia–phosphate cement mortar, Cem.
Concr. Res. 31 (2001) 455–465.
[33] H.B. Tan, X.F. Deng, B.Q. Gu, Effect of borax and sodium tripolyphosphate on
fluidity of gypsum paste plasticized by polycarboxylate superplasticizer,
Constr. Build. Mater. 176 (2018) 394–402.
[34] M. Zajac, J. Skocek, F. Bullerjahn, Effect of retarders on the early hydration of
calcium-sulphoaluminate (CSA) type cements, Cem. Concr. Res. 84 (2016) 62–
75.