Cement and Concrete Composites 104 (2019) 103357

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Cement and Concrete Composites

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A novel bio-inspired bone-mimic self-healing cement paste based on T

hydroxyapatite formation
Qiu Lia, Zhilin Liub, Wanyu Chenb, Bo Yuanb, Xiang Liub, Wei Chena,*
a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, 430070, Wuhan, Hubei, PR China
b
School of Materials Science and Engineering, Wuhan University of Technology, 430070, Wuhan, Hubei, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: A novel bone-mimic self-healing cementitious material was developed by mimicking the healing process of
Hydroxyapatite bionic bone fracture using hydrogel impregnated with phosphate in Portland cement paste. The properties of
Self-healing cement paste phosphate-incorporated hydrogel, feasibility of hydroxyapatite formation in pore solution, release of phosphate
Bone-mimic from the hydrogel into cement paste, phase assemblage of self-healing products in the crack of cement paste and
Hydrogel
the self-healing efficiency were investigated with a range of analytical techniques. The phosphate-incorporated
hydrogel can release phosphate into cracks at controlled rate. Carbonated and calcium deficient hydroxyapatite
particles with sizes of approximately 30 μm were found as the main phase assemblage in the cracks during the
self-healing process. The healing products grew from the surface of both sides to the center of crack. The
compressive strength and impermeability of the self-healing cement pastes containing hydrogel impregnated
with phosphates were fully restored after being cured for 28 days. The autonomous self-healing by introducing
phosphate in hydrogel contributed the most to healing capacity, followed by the autogenous self-healing driven
by the water released from hydrogel and the autogenous self-healing of cement paste. The hydroxyapatite-type
products intermixed with minor amounts of calcite formed in the cracks accompanying the controlled release of
phosphate from the hydrogel, providing the self-healing capabilities of the cement paste.

1. Introduction recovered by the autonomous healing process is usually much higher

Self-healing cementitious materials have the ability to repair the
structural damage autonomously [1,2]. The self-healing processes of
cement paste are classified into two main processes, i.e. the autogenous
healing and the autonomous healing processes, according to their dif-
ferent mechanisms [3]. Autogenous healing is a natural phenomenon in
cement paste owing to hydration of unreacted cement particles and
formation of hydration products in the cracks. The reaction products
that contribute to the autogenous self-healing are found to be Ca(OH)2,
CaCO3 and calcium silicate hydrates (C–S–H) [4]. The hydration of
unreacted cement particle plays an important role in the autogenous
healing process. The maximum width of crack healing is about 300 μm
for a concrete specimen cracked at 28 days and then cured in water at
room temperature for 100 days [5]. The autonomous healing is an ar-
tificial self-healing process, which is usually implemented by in-
corporating chemical or biological agents in the matrix of concrete
[3,6]. Typical examples are bacteria-based self-healing concrete [7],
shape memory alloy-based self-healing concrete [8] and vascular net-
work self-healing concrete [9]. The maximum crack width that can be
than that of the autogenous healing [7,10,11].
Self-healing cementitious materials have been intensively in-
vestigated in the past decades [7,12,13]. Cracks up to of 500 μm in
width can be repaired in self-healing concrete prepared with hydrogel
encapsulating carbonate-precipitating bacteria by formation of calcite
[14,15]. The self-healing process includes both autogenous one attrib-
uted to hydrogel and autonomous one due to the formation of calcite by
bacteria. Superabsorbent polymers are used in self-healing concrete for
autogenous healing of crack [16]. Porous concrete with entrapped
polyvinyl alcohol epoxy is developed to imitate the self-healing process
of bone, where epoxy is infused into the porous network to fill up voids
and to seal cracks in the concrete [17], classified as autonomous self-
healing. The concept of self-healing is initially derived from the phe-
nomenon of biological restoration, and bone-mimic materials are de-
veloped mimicking bone tissue's structure or composition to establish
the self-healing capabilities [18].
Hydroxyapatite (Ca10(PO4)6(OH)2) is a natural crystalline mineral
with hexagonal crystal structure and a calcium to phosphate (Ca/P)
ratio of 1.67 (Fig. 1). Bioactive composites from reactions between

*
Corresponding author.
E-mail address: chen.wei@whut.edu.cn (W. Chen).

https://doi.org/10.1016/j.cemconcomp.2019.103357
Received 22 February 2019; Received in revised form 21 June 2019; Accepted 25 June 2019
Available online 26 June 2019
0958-9465/ © 2019 Elsevier Ltd. All rights reserved.
Q. Li, et al.
Fig. 1. Hexagonal crystal structure of hydroxyapatite (Ca10(PO4)6(OH)2) with a
Ca/P ratio of 1.67. Reproduced from Ref. [57].
hydroxyapatite and composite matrix (zirconia) are developed, which
are 5–7 times stronger and 4–7 times tougher than monolithic hydro-
xyapatite ceramics [19]. Synthetic hydroxyapatite is an ideal bone re-
pair materials, owing to its advantageous properties such as good
compatibility, stability, bioactivity, bone reconstruction and biode-
gradable [20,21].
The bionic bone mineral is essentially nonstoichiometric carbonated
calcium deficient hydroxyapatite (CCDHA), derived from the calcium
deficient hydroxyapatite (CDHA). CDHA has normally a Ca/P ratio of
about 1.5, which is chemically and compositionally similar to stoi-
chiometric hydroxyapatite (Ca/P = 1.67). The low Ca/P ratio of CDHA
originates from the loss of Ca2+ ions from the unit cell [22]. The PO43−
in CDHA can partially be substituted by other elements (Cl−, F−) and
groups (HPO42−, CO32−) (Fig. 2) [23]. Chemical formula of CDHA can
be represented as the following forms [24].
Ca10-x(HPO4)x(PO4)6-x(OH)2-x(H2O)x (x < 1)
Ca9-x (HPO4)1+2x(PO4)5-2x(OH)•2H2O (x < 1)
The structure of CCDHA still remains subject to uncertainties since
the exact location of carbonate ions have not yet been determined. The
numerous possibilities of charge unbalance caused when CO32− ions
enter the structure of CDHA have not been fully clarified [25]. The
carbonate content (CO32−) in a bone mineral is typically 5–8wt%
[26,27]. When the carbonate group substitutes phosphate, the me-
chanical property of hydroxyapatite is improved [28].
CCDHA can be divide into two types based on the position of car-
bonate in the structure. If the carbonate (CO32−) substitutes the hy-
droxyl group (OH−), it is named as A-type, which is a crystalline ma-
terial. The A-type usually forms via reaction of hydroxyapatite with CO2
Fig. 2. Schematic illustration of CO32− substitutions for OH− or PO43− group
in hydroxyapatite (HAp) to form A-type or B-type CCDHA. Reproduced from
Ref. [51].
Cement and Concrete Composites 104 (2019) 103357
gas at high temperature [29]. If the carbonate group substitutes phos-
phate group (PO43−), the product is named as B-type [30]. The B-type
CCDHA is usually formed as a precipitation with a reduced crystallinity.
The morphology of B-type product at ambient temperature is usually
spheroidal. The concentration of carbonate ion can affect the type of
CCDHA. If the concentration of CO32− is low, CO32− can substitute
both hydroxyl and phosphate sites. The B-type substitution is more
usual with high carbonate concentrations [30]. The bionic bone con-
tains both A and B types CCDHA, with the B-type CCDHA dominating
[31].
If a bone tissue is damaged, new CCDHA is formed and repairs the
fracture [22]. The formation of CCDHA is related to factors including
temperature, the value of pH and Ca/P ratio [32]. CCDHA is the most-
likely product between calcium and phosphates if the pH value of the
reaction solution is between 9 and 13 [33]. Amorphous calcium car-
bonate can act as precursor of CCDHA [34,35]. It is therefore possible to
use amorphous calcium carbonate in the cementitious materials to form
CCDHA and to repair the cracks in concrete.
Hydrogels are used as carriers of healing agents to mitigate the si-
multaneous release of self-healing agents into concrete during the
preparation process of fresh concrete [14]. Hydrogel has a network
structure composed of hydrophilic polymers, such as polyvinyl alcohol,
sodium polyacrylate, acrylate polymers [36]. Hydrogels are capable of
sensing the changes of pH or ion concentration in the surrounding so-
lution and release the loads as response to the changes [37]. Hydrogels
were used for developing an autogenous self-healing cementitious
material that release water into the cement paste [38,39]. By using
hydrogel and fly ash, cracks with a width of 300 μm was healed by
93.15% and permeability was restored by 92.4% in an autogenous self-
healing mortar specimen cracked at 28 days and being curing for an-
other 28 days in water under room temperature [40].
In this study, a novel bio-inspired bone-mimic self-healing ce-
mentitious material is developed by using a hydrogel impregnated with
phosphate as the healing agent. The aim is to form hydroxyapatite-type
minerals as healing products in the cracks with controlled release of
phosphate during the self-healing process. The self-healing mechanism
of bone-mimic self-healing cement paste in this study is shown in Fig. 3.
(1)
When a crack is initiated in the bone-mimic self-healing cement paste,
(2) the phosphate in the hydrogel is released into the pore solution in the
crack due to the change of osmic pressure. Water and carbon dioxide
penetrate into the crack and form HCO3−. The Ca2+ and OH− ions in
the pore solution react with phosphate ion and HCO3− to form CDHA/
CCDHA that can heal the cracks.
The structure and phosphate-releasing behavior of hydrogel, the
Fig. 3. Schematic illustration of self-healing process in bone-mimic self-healing
cement paste. After the formation of crack in cement paste, water and CO2 in
the atmosphere penetrated in the cracks, resulting in the swelling of hydrogel
and releasing of phosphate from hydrogel into pore solution. Phosphate reacts
with Ca2+, OH− and HCO3− in pore solution to form hydroxyapatite type
minerals and calcite in the cracks, resulting in the self-healing of cement paste.
2
Q. Li, et al.
Table 1
Oxide composition of ordinary Portland cement.
Oxide Al2O3 SiO2 Fe2O3 CaO K2O SO3 Na2O MgO
Fraction (wt 5.86 21.50 2.85 59.81 0.67 2.06 0.20 2.23
%)
Note: †, LOI: Loss on ignition at 1000 °C.
reaction products of phosphate released from the hydrogel in simulated
pore solution, the phase assemblage and microstructure of self-healing
products are investigated. The effects of self-healing process on the
mechanical properties and permeability of self-healing cement paste are
evaluated.
2. Materials and methods
2.1. Materials
An ordinary Portland cement complying with the Chinese standard
GB 175–2016 classified as P.O. 42.5 (Huaxin Cement Co., Ltd) with
mean particle size of 12.96 μm, fineness of 0.437 m2/g and specific
gravity of 3.05 g/cm3 was used in this study. The oxide compositions of
cement determined with X-ray fluorescence spectrometry (XRF,
PANalytical Axios advanced) are listed in Table 1.
Sodium hydroxide (NaOH), sodium carbonate (Na2CO3), Na2HPO4,
sodium chloride (NaCl), sodium dodecyl sulfate (SDS), acrylic acid
(AA), octadecyl methyl acrylate (OMA), N,N-methylene BIS acrylamide
(BIS) and ammonium persulfate (APS) were used in synthesis of hy-
drogel. N2 gas with purity of 99.99% and HCl solution with a pH value
of 2 were used. All chemicals are AR grade. De-ionized water boiled for
1 h to remove the entrapped gas was used in experiments of synthe-
sizing hydrogel and preparing cement paste.
2.2. Specimen preparation
2.2.1. Synthesis of phosphate-containing hydrogel
The details of method for synthesizing hydrogel in this study fol-
lowed the method in Ref. [41]. Firstly 3.2 g of NaCl and 8 g of SDS were
simultaneously dissolved in 100 ml water, and then 3 g of OMA were
added in the solution. The suspension was then consistently stirred for
4 h at 35 °C after which a clear solution was obtained. Twenty grams of
Na2HPO4 was then added into the solution, bubbled with N2 gas for
20 min. Twenty grams of AA were added into the solution followed by
stirring for 10 min and bubbled with N2 gas for 30 min 0.2 g of BIS and
0.6 g of APS were added into the solution which was further cured in a
sealed flask for 4 h. The obtained gel was dried under vacuum and
grinded with a ball mill at a speed of 400 r/min for 40 min. The ob-
tained powder is termed as hydrogel with impregnated phosphate (HP)
throughout this study. The particle size distribution of the HP measured
with a particle size analyzer (Malvern, Mastersizer 2000) is shown in
Fig. 4.
The Na2HPO4 content in the HP was tested by using the incineration
and dissolution method. One gram of HP was calcined in a muffle
furnace at 700 °C for 2 h and the residue was dissolved in 200 ml HCl
solution with a pH value of 2. The suspension was stirred until all the
residue dissolves and a clear solution was obtained. The concentration
of phosphate in the solution was then analyzed with an inductively
coupled plasma optical emission spectrometry instrument (ICP-OES,
Teledyne Leeman Labs, Prodigy7) with which the total amount of
phosphate was obtained. The mass percentage of Na2HPO4 was 14.4%
in HP powder synthesized in this study. The amount of phosphate in HP
is close to the highest possible content of phosphate due to the limit of
solubility of Na2HPO4 in water (218 g/L at 20 °C).
Hydrogels without impregnating phosphate (termed as HF) was
synthesized with the same procedure but without addition of Na2HPO4.
Cement and Concrete Composites 104 (2019) 103357
LOI†
3.70
Fig. 4. Particle size distributions of HP after being ball milled for 40 min. The
arrows indicate the axis related to the curve.
2.2.2. Specimens for formation of hydroxyapatite in pore solution
Formation of hydroxyapatite in pore solution of cement paste was
investigated by immersing fractured hardened cement paste in pore
solution with 2 g of HP. The setup of the experiment is shown in
Fig. 5(a). Two grams of HP hydrogel in a bag made of permeable
membrane was suspended in the pore solution to provide the source of
phosphate, which is released from the hydrogel. The fresh surface of the
fractured hardened cement paste was expected to provide consistent
Ca2+ through leaching out of the paste.
The pore solution was obtained with a cement slurry containing 50 g
cement and 500 g deionized water. The cement slurry was mixed with
water with a Hobart mixer for 120 s and then consistently stirred with a
magnetic stirrer for 1 h in a sealed beaker. The slurry was then filtered
in vacuum with N2 gas protection, after which the filtrate was collected
and pore solution was obtained.
To prevent the unfavorable precipitation of Ca3(PO4)2 or hydro-
xyapatite caused by reaction of Ca2+ in pore solution with phosphate
released from HP hydrogel, Na2CO3 was added in the obtained pore
solution to remove Ca2+ according to Eq. (1). The concentration of
Ca2+ in the obtained pore solution was measured with ICP-OES.
Na2CO3 were then added in the obtained pore solution with stirring in a
sealed container till all Ca2+ in the solution is precipitated. The sus-
pension was then filtered to obtain the pore solution used in this study.
The pH value the pore solution was 12.5, measured with a digital pH
meter.
Ca2 + + Na2 CO3 → CaCO3 + 2Na+ (3)
Fresh plain cement pastes were prepared by mixing OPC with water
with a w/c ratio of 0.35. The fresh paste is casted into moulds with sizes
of 40 × 40 × 40 mm3 and cured for 28 days at 20 °C and 95% RH. The
hardened specimens were fractured with a compression machine by
splitting the cubic specimens with an iron bar (5 mm in diameter) lying
on the top of the specimens (Fig. 5(b)). Four sides of cubic specimens
were wrapped with aluminum tapes before being split to prevent dis-
integration of specimens.
The hardened cement paste was transferred into a beaker and im-
mersed in the pore solution with the fresh fractured surface on top. A
layer of white precipitate appeared on the fresh fractured top surface of
hardened cement paste after 8 h, and the amount consistently increased
afterwards. The paste specimen with the white precipitate on top was
moved out of the pore solution at 3 days and placed into a beaker filled
with de-ionized water. The beaker with the specimen was agitated with
ultrasonic dispersion and the suspended powders in the solution was
collected through centrifugation. The collected white precipitate was
then dried and transferred for analysis.
2.2.3. Specimens for diffusion of phosphate out of HP and formation of
hydroxyapatite
Sandwich specimens with interlayered HP powder between plain
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Q. Li, et al.
Fig. 5. Schematic illustration of setup for (a) the precipitation of hydroxyapatite in pore solution on hardened cement paste, (b) splitting the hardened cement paste
and(c) the preparation of sandwich specimens with interlaid HP powder.
cement pastes without HP were prepared to investigate the diffusion of
phosphate out of HP and its effects on the formation of hydroxyapatite
(Fig. 5(c)). Plain cement paste without hydrogel was casted into the
cubic mould (40 × 40 × 40 mm3) with a layer thickness of 20 mm.
Four grams of HP powder were then manually dispersed on top of the
fresh paste followed by slightly tapping the mould. The cubic mould
was then filled with plain cement paste without hydrogel again. The
specimens were split along the HP powder layer after being cured for 7,
14, 21 and 28 days and the fresh fractured surface of the interface were
transferred for analysis. Powders at the interlayer surfaces were also
collected by brushing the fresh fractured surface. The obtained powders
were then further analyzed. Specimens of the remaining plain cement
paste away from the interlayer surface were also collected, which was
finely ground to powder with particle size smaller than 80 μm and
freeze dried before analysis.
2.2.4. Specimens for self-healing capability test
Three types of cement pastes with a water to cement ratio (w/c) of
0.35 are prepared, containing 3% HP, 3% HF or without hydrogel. All
the mass fractions are the fractions of hydrogel to the mass of cement.
The fresh cement paste was mixed with a Hobart mixer for 120 s and
casted into different moulds followed by manual vibration for 30 s. The
size of the cubic specimens was 40 × 40 × 40 mm3 for compressive
strength tests and those of the cylinder specimens were 75 mm in dia-
meter and 50 mm in height for water permeability tests. All specimens
were demoulded after one day and followed by further curing at 20 °C
and 95% RH. The total curing age was 28 days. The compressive
strength and water permeability of the intact specimens were then
tested.
The cubic and cylinder specimens were loaded with a compression
machine to generate cracks in the specimens at 28 days. The load ap-
plied in the cracking process was 85% of the ultimate compressive
strength at 28 days and lasted for 20 s. The residue compressive
strength of cubic specimens with cracks are then tested again with the
same compression machine. Specimens with cracks were transferred to
the curing chamber at 20 °C and 95% RH and cured for another 7, 14,
4
Cement and Concrete Composites 104 (2019) 103357
21 or 28 days, after which the compressive strength and water per-
meability of the specimens were tested.
2.3. Test procedure and analytical techniques
2.3.1. Structure, diffusion and swelling properties of hydrogel
The structure of hydrogel and bonding of phosphate in hydrogel was
analyzed with Fourier Transform Infrared Spectroscopy (FTIR).
Diffusion rate of phosphate out of HP into the surrounding liquid is
essential for providing the self-healing capability. It is closely related to
the swelling rate of the HP [42]. In this study, the HP were immersed in
deionized water, pore solution and solution of NaOH (0.01 M, pH = 12)
in sealed container, respectively, to characterize the diffusion rate of
phosphate and the swelling property of hydrogel.
The diffusion rate of phosphate was measured with the following
steps. Two grams of HP were put into the bag made of permeable
membrane and the weight was recorded. The bag containing the HP
was then suspended in 500 ml liquid of deionized water, pore solution
or NaOH solution. The solutions were consistently stirred with a mag-
netic stirrer in sealed beakers. The concentration of phosphate in the
solution was measured with Inductively Coupled Plasma Optical
Emission Spectrometry (ICP-OES) every 1 h until 40 h. The concentra-
tion of phosphate was afterwards calculated. The diffusion rate of
phosphate was calculated with the following equation.
mt
R= × 100%
m0 (4)
where R (%) is the diffusion rate of phosphate at time of t, mt (g) is the
total phosphate released from hydrogel at time of t, and m0 (g) is the
total phosphate content in the initial hydrogel.
The swelling property of hydrogel was tested as follows. Two grams
of hydrogel were mixed with 500 ml deionized water, pore solution or
NaOH solution in sealed beakers. The hydrogel was repeatedly taken
out every 30 min and surface dried, and weighed until constant weight.
The swelling property of hydrogel was calculated as follows.
Q. Li, et al. Cement and Concrete Composites 104 (2019) 103357

wt − w0 as
SR = Hs = × 100%
w0 (5) a0 (7)

where SR (g/g) is the swelling rate of hydrogel, wt (g) is the weight of where Hs (%) is the self-healing efficiency of properties; as is the
hydrogel at time of t, and w0 (g) is the initial weight of hydrogel. compressive strength (MPa) or water permeability (mm/s) of specimens
after self-healing at various ages; a0 is the compressive strength (MPa)
or water permeability (mm/s) of intact specimens at the same age.
2.3.2. Structure of self-healing products in cement paste
To evaluate the feasibility of formation of hydroxyapatite in the
2.3.4. Statistical significance of self-healing efficiency
pore solution in cracks, the white precipitate on the freshly fractured
To evaluate the statistical significance of effect of introducing
surface of hardened cement paste in pore solution in Fig. 5(a) was
phosphate into hydrogel on the self-healing of cement paste, the student
transferred for analysis with X-ray powder diffraction (XRD), FTIR,
t-test was performed on the self-healing efficiency of plain cement
Raman spectroscopy and scanning electron microscopy with energy
paste, cement paste with HF and those with HP. The p value was cal-
dispersive X-ray spectroscopy (SEM-EDX). The aim is to obtain the
culated by TTEST function in Microsoft Excel 2016. When p value is
microstructure and chemical composition of white precipitate, so as to
lower than α = 0.05, the difference between self-healing efficiency is
evaluate the feasibility of bone-mimic self-healing methodology.
significant. And when p value is lower than α = 0.01, the difference is
The fine powders of hardened cement paste around or away from
extreme significant. Otherwise the difference is statistically non-sig-
HP in Fig. 5(c) were transferred for XRD analysis to assess migration of
nificant.
phosphate out of HP in an intact specimen. The reaction products
containing phosphate formed in the hardened cement paste near HP are
analyzed and compared to the products in the hardened cement paste 3. Results and discussion
away from HP.
XRD analysis was conducted with Rigaku MiniFlex600 powder X- 3.1. Structure and properties of hydrogel
ray diffractometer with a Cu Kα (λ = 1.54 Å) incident radiation under
the condition of range of 5°–60°, step size of 0.02° 2θ/step and mea- The FTIR spectra of HF and HP hydrogels are shown in Fig. 6. The
suring time of 0.24 s/step. The fresh paste specimens were ground to peak around 990 cm−1 corresponds to PO43− vibrational band in-
fine powder passing 0.063 mm sieve before transferred for analysis. dicating that part of HPO42− transformed into PO43−. The peak at
Approximately 1 g of specimen was back-loaded in the sample holder. 875 cm−1 corresponds to HPO42− [22] and CO32−, which could be due
FTIR analysis was performed on the fresh finely-ground powder of to the absorption of CO2 in the atmosphere during the synthesis. It is
specimens with Thermo Nicolet Nexus FTIR under the attenuated total notable that this peak was not observed in the spectrum of HF, in-
reflectance (ATR) mode in the range of 4000–400 cm−1 with a re- dicating that is more likely from HPO42−. Other peaks in HP are similar
solution of 4 cm−1. to those in the hydrogel without phosphate. The peaks at 1566 and
Raman spectroscopy was used to characterize the phase assemblage 1405 cm−1 correspond to the C=O antisymmetric and symmetric
on Horiba LabRAM HR Evolution Raman spectrometer with a 532 nm stretching absorptions due to the COO− group. The type of bonding of
laser source at a power of 3 mw. The spectra were acquired in the range phosphate with hydrogels could be hydrogen bond. When –COOH was
of 300–1500 cm−1. The specimens were observed at 20 °C with an dissociated to –COO-, the increased polar bonds may repel the negative
optical microscope with an Olympus LMPLFLN 50 × objective lens. charges [16], which could prevent the strong association of PO43− or
SEM images of cement pastes were obtained with FEI Quanta HPO42−. These results indicated that the phosphate was successfully
450FEG scanning electron microscopy with secondary electron and impregnated in the hydrogel.
backscattered electron mode (acceleration voltage 20 kV). Chemical The diffusion rate of phosphate in hydrogel into various solutions
compositions of hydration and healing products were characterized by are shown in Fig. 7(a). The phosphate in hydrogels diffused rapidly into
EDX. Specimens were dried and coated with Pt before transferred to the solutions in the first 5 h and then the diffusion rate gradually decreased.
sample holder. The diffusion rate is approximately 1.5 mM/L·h in the beginning, and
then reduced to 0.033 mM/L·h. The highest diffusion rate was found in
the deionized water, followed by NaOH solution and pore solution. The
2.3.3. Self-healing capability of cement paste highest release rate of phosphate ions from the hydrogels in deionized
The capability of self-healing was evaluated by comparing the water is the result of the difference in the osmotic pressure due to the
compressive strength or water permeability of specimens with cracks to different ionic strength of the different solutions [43]. The osmotic
those after self-healing. The compressive strength was tested with cubic pressure for hydrogels immersed in deionized water is relatively higher
specimens using compression machines according to Chinese standard
GB/T 17671–1999. Three specimens were tested for each batch. The
compressive strength was calculated with the average of three speci-
mens, together with the standard deviation. After breaking of healed
specimens, the powder at the fractured surface was collected by
brushing.
Water permeability was performed on three vacuum saturated
specimens in each batch according to Chinese standard GB/T
25993–2010. The water permeability was calculated as the average of
three specimens, according to the following equation.
QL
kT =
AHt (6)

where kT (mm/s) is the permeability at temperature of T, Q (ml) is the

water permeated through the specimen during time of t, L (mm) is the
thickness of the specimen, A (mm2) is the area of top of cylinder, H
(mm) is the difference of water level and t (s) is the time of test.
The self-healing capability of properties was calculated with the Fig. 6. FTIR spectra of synthesized HF and HP hydrogels. The peaks at 875 and
following equation. 990 cm−1 indicate the incorporation of phosphate in HP hydrogels.

5
Q. Li, et al.
Fig. 7. Diffusion and swelling properties of HP in various solutions. (a) Diffusion of phosphate ion; (b) swelling properties of hydrogel. HP hydrogel had the lowest
diffusion and swelling in pore solution, followed by in NaOH solution and in deionized water.
than those in NaOH solution and pore solution, resulting in a higher
release rate of phosphate ions, especially in the first 10 h. The osmotic
pressure gradually decreased after releasing approximately 80% of
phosphate from hydrogel. The total release rates of HP in three solu-
tions are similar after 25 h (approximately 93%). The highest total re-
lease rate was observed with HP in deionized water, followed by pore
solution and NaOH solution after 40 h of release.
The swelling ratio of the hydrogel in deionized water is about
19.4 g/g, which is similar to that in NaOH solution and much higher
than that in pore solution (9.45 g/g) (Fig. 7(b)). The reason is that the
osmotic pressure in pore solution of hydrogel was relatively lower than
those in deionized water and NaOH solution [16,44]. In general, high
swelling ratio of HP is associated with promoted diffusion rate of
phosphate out of HP. Although the swelling ratio of HP in pore solution
was much lower than those in deionized water and NaOH solution at
35 h, the diffusion rate of phosphate at the same time were similar.
3.2. Structure of CDHA formed in pore solution
SEM images of reaction products on the top of fractured cement
paste samples immersed in suspensions of pore solution and HP are
shown in Fig. 8(a). Clusters of products with a size of approximately
10 μm were observed over the surface of hardened cement paste, which
was consisted of anisotropic 10–50 nm needle crystallites and was si-
milar to the morphology of hydroxyapatite found in bone tissue in lit-
erature [45].
The XRD pattern of the reaction products formed in the pore solu-
tion is shown in Fig. 8(b). CDHA was identified in the precipitated
products, structure of which is similar to the products formed with a
continuous microwave method [46]. The formation of CDHA was due
to the lack of calcium ions on the surface of hardened cement paste
6
Cement and Concrete Composites 104 (2019) 103357
specimens, resulting in a lower Ca/P in hydroxyapatite. The broad peak
width of XRD pattern suggested the low crystallinity nature of the
precipitated products due to the calcium deficiency in CDHA structure.
No peaks of calcium hydroxide, calcite or calcium phosphate is iden-
tified.
Chemical composition of CDHA formed on the surface of hardened
cement paste in pore solution containing HP was characterized with
SEM-EDX (Fig. 9), and the Ca/P ratios at three typical positions is close
to 1.5. The formula of CDHA formed in this study was calculated as
follows.
Ca9(HPO4)(PO4)5(OH)(H2O) (8)
The FTIR spectra of products formed on the surface of hardened
paste in pore solution are shown in Fig. 10(a), which show all the
characteristic absorption bands of CDHA. The absorption bands at
1040 cm−1 was attributed to PO43− stretching vibration, and the de-
formation vibration of the PO43− appeared at 562 cm−1 and 601 cm−1.
Peak at 880 cm−1 was assigned to the HPO42− and CO32−, confirming
the formation of CDHA and calcite. The band at 966 cm−1 was due to
the stretching band of PO43−, which could be used to distinguish CDHA
from the beta tricalcium phosphate (β-TCP) [21], due to the fact that
the stretch band of PO43− in β-TCP was at 947 cm−1. The bands at
1648 cm−1 and 3421 cm−1 were corresponding to the absorbed water
in CDHA. The band at 3565 cm−1 was corresponding to –OH, which is
too small to identify because CDHA shows low intensity –OH stretching
and vibrational bands than stoichiometric hydroxyapatite [22]. The
peaks at 1423 and 1485 cm−1 originated from the CO32− group, due to
the formation of calcite and CCDHA in the specimen, where the –OH
and PO43− in CDHA were partially occupied by CO32− [47]. According
the previous study on the XRD pattern of CDHA, the PO43− in CDHA
could be partially occupied by CO32− [48]. These results confirm the
Fig. 8. SEM image and XRD pattern of reaction
products formed on the surface of hardened cement
paste immersed in pore solution after 3 days. (a)
SEM secondary electron image indicates the for-
mation of clusters of products in size of 10 μm,
consisting of anisotropic 10–50 nm needle crystal-
lites which is similar to the morphology of hydro-
xyapatite found in bone tissue; (b) calcium deficient
hydroxyapatite (CDHA) was identified as reaction
products according to XRD pattern.
Q. Li, et al.
Fig. 9. Ca/P atomic ratio of CDHA formed on the surface of plain hardened paste immersed in pore solution with HP particles at 3 days characterized with SEM-EDX.
The decrease of Ca/P from 1.67 in hydroxyapatite to approximately 1.50 was due to the deficiency of calcium in the structure.
feasibility of forming CCDHA on the fresh surface of hardened cement
paste with the presence of HP and pore solution.
The Raman spectrum of precipitated products on the surface of
hardened cement paste is shown in Fig. 10(b). The band at 428 cm−1
was due to ν2 PO43−. The 579 cm−1, 593 cm−1 and 608 cm−1 bands
were attributed to ν4 PO43−. The strong band at 960 cm−1 was corre-
sponding to the ν1 PO43−. A band at 1047 cm−1 was associated to ν3
PO43−. The band at 1071 cm−1 showed the B-type sites CO32− in
CCDHA. The band at 1003 cm−1 originated from the ν1 HPO42−. The
very weak band at 878 cm−1 derived from the (P–OH) stretching of
HPO42− ions. These results show that the precipitated products was B-
type CCDHA, where CO32− groups substitute phosphate sites, which
agrees well with the FTIR pattern [49,50]. The A-type CO32−, which
would appear at 1106 cm−1 if there was any, was not detected, in-
dicating that CCDHA formed was B-type only. The formation of B-type
is more favorable in the solution environment, which is the case in this
study, whereas A-type is preferred in the high temperature environment
with dry CO2 gas [29,30,51].
3.3. Diffusion of phosphate out of hydrogel in cement paste
One of the important characteristics of self-healing cement paste is
that the healing agent can sponteneously respond to the formation of
cracks to form healing products. The healing agent should remain stable
in the intact material. Cracking of material triggers the release of
healing agent into the cracks. This property is also named self-sensing.
To characterize the self-sensing properties of bone-mimic self-healing
cement paste in this study, the hydration products around and away
from a the HP hydrogel layer embedded in the sandwich-structured
hardened cement paste (Fig. 5(c)) were characterized with XRD ana-
lysis.
The XRD patterns of the hardened cement pastes arround or away
7
Cement and Concrete Composites 104 (2019) 103357
from the HP hydrogels at 7, 14, 21 and 28 days are shown in Fig. 11.
Portlandite and ettringite were identified in both speciemens at all ages,
which are hydration products of OPC. Alite, larnite and calcite were
also identified, which are anhydrous phases and admixture from Port-
land cement. There was no CDHA phase identified in the pastes either
around or away from HP, indicating that phosphate was not released
from HP hydrogel when there was no crack formed in the cement paste.
Hydroxyapatite has the lowest solubility and is the most stable phase
among all phosphate phases when pH is over 4.2 [52]. Hydroxyapatite
should be identified if the phosphate in the hydrogel was released
during the mixing or curing. These results confirmed that no phosphate
was released out of HP in the intact cement paste. specimens.
3.4. Self-healing capability of cement paste with HP
Images of cement paste containing HP after cracking at 28d and
healing for 28d is shown in Fig. 12. Reaction products were clearly
observed, which filled the cracks. Compressive strength of intact ce-
ment pastes and those with cracks is plotted in Fig. 13(a)-(c). Adding
hydrogel lowers remarkably the compressive strength of cement pastes
at 28 days. The compressive strength of the plain cement paste, paste
containing HF and that containing HP was 66.42, 31.27 and
33.0 MPa at 28d, respectively. The residue compressive strength of ce-
ment pastes after applying a compressive pressure of 85% of the ulti-
mate strength for 20 s is 50.20, 21.85 and 22.95 MPa, respectively.
The compressive strength of plain cement paste is gradually restored
with the increase of further curing after cracking, from 50.2 MPa after
cracking at 28 days to 55.80 MPa after curing for another 28 days under
standard curing conditions. The self-healing capability of plain cement
paste without hydrogel is 81.8%.
The compressive strength of cement pastes with 3% HF (by weight)
gradually increased with healing ages, from 21.85 MPa after cracking at
Fig. 10. (a) FTIR and (b) Raman spectra of products
formed on the surface of fresh plain paste immersed
in pore solution with HP particles. The peaks at 966
and 880 cm−1 in FTIR spectrum indicates the for-
mation of CDHA and calcite. The band at
1071 cm−1 in Raman spectrum shows the B-type
sites CO32− in CCDHA, and the absent of band at
1106 cm−1 indicates that no A-type CCDHA was
identified.
Q. Li, et al.
Fig. 12. Image of self-healed cracks in cement paste containing HP, which was
cracked at 28 days and cured for another 28d under standard curing conditions.
28 days to 26.13 MPa after healing for 28 days. The self-healing cap-
ability of HF specimens was 80.3% after curing for another 28 days,
with an increase of compressive strength of 4.3 MPa.
The compressive strength of cement pastes with 3% HP (by weight)
increased steadily with healing ages from 22.85 MPa after cracking to
33.50 MPa after curing for another 28 days. The self-healing capability
was 98.2% and 96.3% after curing for another 21 and 28 days, with an
increase of compressive strength of 10.3 and 10.6 MPa, respectively.
The healing efficiency of various cement pastes is plotted in
Fig. 13(d). The self-healing process in the CP and HF specimens can be
classified as autogenous self-healing, and that in the HP specimens can
be classified as autonomous self-healing. By comparing the percentage
of restoration of compressive strength, addition of HF contributed
8
Cement and Concrete Composites 104 (2019) 103357
Fig. 11. XRD patterns of hardened cement pastes
around (ar) and away (aw) from HP hydrogel at the
curing age of (a) 7, (b) 14, (c) 21 and (d) 28d. The
peak positions for CDHA are shown on the bottom,
indicating the absence of CDHA in cement paste.
The mineral phases were the same in all specimens,
indicating phosphate was not release into cement
paste without cracking.
approximately 4.2% of self-healing capability on the basis of auto-
genous self-healing of cement paste. Introducing phosphate in the hy-
drogel contributed 19.2% of autonomous self-healing capability on the
basis of autogenous self-healing of HF and cement paste. These results
indicate that the specimens were successfully self-healed through the
autonomous self-healing process.
The water permeability of specimens after self-healing at various
ages are shown in Fig. 14. After cracking at 28 days of curing under
standard conditions, the water permeability of CP, HF and HP speci-
mens were 0.54 mm/s, 0.70 mm/s and 0.63 mm/s.
For cement paste without addition of hydrogel (CP), the water
permeability gradually decreased with the increase of further curing,
from 0.54 mm/s after cracking to 0.46 mm/s after curing for another 28
days under standard curing conditions, which is still high for cement
paste. The reduction of water permeability of CP specimen was
0.08 mm/s after curing for another 28 days.
For cement paste with 3% HF, the water permeability decreased
dramatically from 0.70 mm/s to 0.32 mm/s after curing for 7 days, and
gradually decreased afterwards to 0.27 mm/s after curing for 28 days
after cracking. The reduction of water permeability of HF specimen was
0.43 mm/s after curing for another 28 days.
For cement paste with 3% HP, the trend was similar to that of HF
specimens. The water permeability dramatically decreased from
0.63 mm/s to 0.13 mm/s after curing for another 7 days, and con-
tinuously decreased with the increase of curing age, to 0.004 mm/s by
curing for another 28 days after cracking. The reduction of water per-
meability of HP specimen was 0.63 mm/s after curing for 28 days after
cracking.
After curing for 28 days after cracking, the reduction of water
permeability of CP, HF and HP specimens were 0.08 mm/s, 0.43 mm/s
and 0.63 mm/s, respectively. By comparing these results, the auto-
genous self-healing by the cement paste contributed a reduction of
0.08 mm/s of water permeability. The autogenous self-healing by
Q. Li, et al.
Fig. 14. Water permeability of specimens after self-healing for different ages.
Three specimens were tested for each age. Error bars indicate the standard
deviation. The statistical significances (p values) between the results from dif-
ferent specimens are shown in Table 2. The cement paste with HP showed the
highest self-healing capacity, followed by cement paste with HF and plain ce-
ment paste. The contribution of self-healing on water permeability was ordered
by highest to lowest as hydrogel, phosphate incorporation, and autogenous self-
healing by cement paste.
addition of HF contributed a reduction of 0.35 mm/s of water perme-
ability on the basis of autogenous self-healing of cement paste. And the
autonomous self-healing by introducing phosphate in hydrogel con-
tributed a reduction of 0.20 mm/s of water permeability on the basis of
autogenous self-healing of cement paste and HF. According to these
results, the autogenous self-healing by addition of hydrogel itself con-
tributed the most to the reduction of water permeability, followed by
autonomous self-healing by introducing phosphate and autogenous self-
healing by cement paste. The reason could be the swelling of hydrogel
through absorption of water, resulting in the blockage of cracks.
Although addition of hydrogel itself contributed the most to the
9
Cement and Concrete Composites 104 (2019) 103357
Fig. 13. Development of compressive strength and
self-healing efficiency of CP, HF and HP specimens
after self-healing at 7, 14, 21 and 28 days, together
with those from control specimens at the same age.
Three specimens were tested for each age. Error
bars indicate the standard deviation. The statistical
significances (p values) between the results from
different specimens are shown in Table 2. (a) Plain
cement paste without hydrogel; (b) Cement paste
with HF; (c) Cement paste with HP; (d) Self-healing
efficiency. Cement paste with HP showed the
highest self-healing efficiency, followed by cement
paste with HF and plain cement paste.
reduction of water permeability, without introducing phosphate in
hydrogel, the water permeability of cement paste after cracking could
not be fully restored to those of the intact specimens.
The p values for the self-healing efficiency of compressive strength
and water permeability are shown in Table 2. According to these re-
sults, the difference of self-healing efficiency of compressive strength is
statistically significant (p < α = 0.05) between three types of speci-
mens, namely CP, HF and HP, indicating that the effect of hydrogel and
phosphate incorporation was different on the self-healing of cement
paste. The difference between HP and HF was statistically extreme
significant (p < α = 0.01), indicating that incorporating phosphate in
hydrogel significantly improved the effect of self-healing on the com-
pressive strength, due to the autonomous self-healing by formation of
hydroxyapatite type minerals in the cracks.
For water permeability, the difference between those of CP and HF
is statistically non-significant. The difference between those of CP and
HP is statistically significant, and that between HF and HP is statisti-
cally extreme significant, indicating that incorporating phosphate in
hydrogel effectively improved the self-healing on the water perme-
ability.
3.5. Self-healing products in cement paste after cracking
The morphology of self-healing products in the crack of cement
Table 2
The p values‡ calculated by student t-test between three types of specimens in
the self-healing efficiency of compressive strength and water permeability.
Self-healing efficiency of compressive strength Water permeability
CP-HF CP-HP HF-HP CP-HF CP-HP HF-HP
p 0.042 0.042 0.009 0.084 0.019 0.003
‡
Note: , p value: the difference between the result is statistically significant
when p < α = 0.05, is statistically extreme significant when p < α = 0.01,
and is statistically non-significant when p > α = 0.05.
Q. Li, et al.
paste after curing for 14 days after cracking is shown in Fig. 15. Calcite
cubes of approximately 20 μm in size and CCDHA spheres of approxi-
mately 30 μm in diameter were observed, which were similar to those
observed in Fig. 8(a). There were more CCDHA than calcite. CCDHA
spheres connected to each other and grew from the both sides of surface
of crack to the center of crack. The dense microstructure of CCDHA
indicates the good mechanical properties. There was flaky structure on
the surface of CDHA spheres, which was nano-sized crystallite of
CCDHA [20]. The calcite crystals intermixed with CCDHA. During the
curing after cracking, CO2 in the atmosphere was introduced into the
pore solution, resulting in the formation of amorphous calcium carbo-
nate [53], which was the precursor of carbonated CCDHA with the
supply of phosphate from hydrogels [34].
FTIR analysis was performed on the self-healing products and the
results confirmed the formation of CDHA/CCDHA and calcite
(Fig. 16(a)). The peak positions were almost the same as those from the
simulated conditions (Fig. 10(a)). The peak at 878 cm−1 corresponding
to HPO42− and CO32− confirmed the formation of CDHA and calcite.
The peak intensities were higher than that from simulated conditions,
indicating the formation of more CDHA and calcite in the cracks in
cement paste. Under the standard curing conditions, the introducing of
CO2 from atmosphere into the pore solution is inevitable, which will in
turn results in the formation of CCDHA. The healing products were a
mixture of CDHA and CCDHA with some amount of calcite.
The XRD pattern and Raman spectrum of self-healing products
formed in the cracks are shown in Fig. 16(b)-(c). Calcite and CDHA
were identified according to XRD pattern, which agrees well with re-
sults from SEM and FTIR. In the Raman spectrum of self-healing pro-
ducts in the cracks, the peaks at 961, 429 and 1086 cm−1 were due to
the ν1 symmetric stretching mode, ν2 bending mode and ν3 antisym-
metric stretching mode of PO43−, respectively. And the peaks at 581,
593 and 610 cm−1 were assigned to the PO43− ν4 mode [54–56], and
the peak at 713 cm−1 was due to the ν4 CO32−. The characterization of
self-healing products by XRD and Raman confirmed the formation of
calcite and hydroxyapatite type minerals, which were a mixture of
CDHA and CCDHA.
10
Cement and Concrete Composites 104 (2019) 103357
Fig. 15. Morphology of self-healing products in the
crack of cement paste after curing for 14 days. (a) a
close look of morphology of CDHA and calcite,
which was spheres with flaky structure on the sur-
face for the former and cubic crystallite for the
latter; (b) connection of CDHA spheres; (c) CDHA
growing from both sides to the center in the crack.
The bone-mimic self-healing cement paste had an effective high
capability in restoring the performances after 28 days of self-healing.
The self-healing process in the bone-mimic self-healing cement paste
was a combination of autogenous self-healing from hydrogel and ce-
ment paste and autonomous self-healing by introducing phosphate
through formation of CCDHA and calcite in the cracks. In regard to the
self-healing capability of compressive strength, the autonomous self-
healing by introducing phosphate in hydrogel contributed the most,
followed by autogenous self-healing by hydrogel itself and autogenous
self-healing by cement paste. In regard to the self-healing capability of
water permeability, the autogenous self-healing by hydrogel itself
contributed the most, followed by the autonomous self-healing by in-
troducing phosphate in the hydrogel and the autogenous self-healing by
cement paste.
4. Conclusion
In this study, a novel bio-inspired bone-mimic self-healing ce-
mentitious material was designed by mimicking the restoration process
of bone fracture through introducing phosphate-incorporated hydrogel
into Portland cement paste. The properties of designed hydrogel, the
feasibility of formation of hydroxyapatite type self-healing minerals in
the pore solution, the diffusion behavior of phosphate in hydrogel into
cement paste, the phase assemblage of self-healing products in the
crack of cement paste and the self-healing efficiency were characterized
by a range of analytical techniques. According to the results obtained,
the following conclusions can be drawn.
The hydrogel incorporates 14.4 wt% phosphate, which can be gra-
dually released into deionized water, sodium hydroxide or pore solu-
tion of cement paste. The release rate is the highest in deionized water
and lowest in pore solution of cement paste.
Calcium deficient hydroxyapatite (CDHA) was formed on the sur-
face of fresh hardened cement paste with presence of pore solution and
phosphate-incorporated hydrogel. CDHA spheres spread over the sur-
face of harden cement paste with anisotropic nano-sized needle crys-
tallites.
Q. Li, et al.
The self-healing products in the crack of bone-mimic self-healing
cement paste were a mixture of CDHA and CCDHA with small amount
of calcite. The CDHA spheres were in size of 30 μm in diameter with
nano-sized flaky crystallite. The dense self-healing products well con-
nected to each other and grew from the sides of crack to the center of
crack.
The self-healing capability of cement paste containing HP gradually
increased with the curing time, and reached 96.3% for compressive
strength and fully restored for water permeability after curing for an-
other 28 days after cracking at 28 days. For self-healing capability of
compressive strength, the autonomous self-healing by introducing
phosphate in hydrogel contributed the most, followed by the auto-
genous self-healing by cement paste and the autogenous self-healing
driven by hydrogel. For self-healing capability of water permeability,
the autogenous self-healing by hydrogel itself contributed the most,
followed by the autonomous self-healing by introducing phosphate in
hydrogel and the autogenous self-healing by cement paste.
Acknowledgement
This research has been financially supported by the National
Natural Science Foundation of China (grant numbers 51672199); the
Fundamental Research Funds for the Central Universities (grant
number WUT: 2017-YB-008); and the National Key Research and
Development Program of China (grant number 2016YFB0303501,
BY115J004) and the 111 Project (No. B18038).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cemconcomp.2019.103357.
11
Cement and Concrete Composites 104 (2019) 103357
Fig. 16. (a) FTIR spectrum, (b) XRD pattern and (c)
Raman spectrum of self-healing products formed in
the crack of cement paste after curing for another 14
days. The peak at 878 cm−1 in FTIR spectrum cor-
responding to HPO42− and CO32− confirmed the
formation of CDHA and calcite, which were identi-
fied and confirmed by XRD pattern and Raman
spectrum.
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