Construction and Building Materials 200 (2019) 36–45

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Construction and Building Materials

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / c o n b u i l d m a t

Activated chemicals of cementitious capillary crystalline waterproofing

materials and their self-healing behaviour
Guangyan Li a, Xiaofeng Huang a, Jiesheng Lin b, Xiang Jiang a, ⇑, Xinya Zhang a, ⇑
a
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China
b
Guangdong Carpoly Greenway Technology Materials Co. Ltd., Jiangmen 529085, Guangdong, China

H I G H L I G H T S

● Sodium carbonate, sodium silicate, sodium aluminate, tetrasodium EDTA and glycine proposed as activated chemicals of CCCW.
● The optimal proportion of activated chemicals of CCCW was achieved through permeability and pre-pressure self-healing test.
● White crystals with an average diameter of 0.2 m m were generated in the self-healing process of CCCW.
● The self-healing mechanism of CCCW was proposed based on the self-healing experimental results.

A R T I C L E I N A B S T R A
F O C T
Article history: Activated chemicals play a key role in the waterproof performance of cementitious capillary crystalline
Received 21 January 2018 waterproofing materials (CCCW). We proposed sodium carbonate, sodium silicate, sodium aluminate,
Received in revised form 14 December 2018 tetrasodium EDTA and glycine as activated chemicals of CCCW. The proportion of activated chemicals of
Accepted 15 December 2018
CCCW was optimized by two key parameters evaluation of the second permeability ratio and pre-
pressure self-healing rate for their self-healing ability of CCCW. Results show that sodium silicate has
the most significant impact on the self-healing ability of CCCW. In the self-healing progress of CCCW,
Keywords:
the consumption of Ca(OH) 2 (CH) and the production of Calcium Silicate Hydrate (CSH) gel, calcium
Cementitious capillary
carbonate and ettringite were observed through XRD and SEM analysis. The white crystals with an
crystalline waterproofing
Activated chemicals average diameter of 0.2 m m are produced on both sides of cracks, and consequently the cracks were
Self-healing healed by the accumulation of crystals. The self-healing mechanism of CCCW was proposed based on the
Permeability self-healing experimental results.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete is widely used as construction materials due to its
high durability and low cost. But the unexpected cracks
caused by construction loading or shrinkage remain a challenge
during varying temperature, commonly leading to a decrease on
concrete strength and exposing the interior of concrete exposed to
the envi- ronment [1]. And concrete is porous, consisting of
tunnel-like cap- illaries, which give access to water and other
unwanted chemicals. As a consequence, concrete is susceptible to
chemical attack, prob- ably ending up with the corrosion of the
inside steel bars [2,3]. In addition, larger cracks are likely to
appear over time and would form a path for water outside, which
not only impair the durability of concrete, but also destroy the
water tightness of the cement structure [4]. The damage of cracks
in buildings caused severe eco-
* Corresponding authors.
E-mail addresses: jiangx@scut.edu.cn (X. Jiang), cexyzh@scut.edu.cn (X. Zhang).
https://doi.org/10.1016/j.conbuildmat.2018.12.093
0950-0618/© 2018 Elsevier Ltd. All rights reserved.
nomic losses [3,5]. According to De Rooij and Van Tittelboom [6],
the UK spends 45% of the annual construction costs to maintain
the existing concrete structure. It is quite imperative to improve
the durability of concrete for both economic and social benefits.
Conventional ways to repair concrete are using polymer mate-
rials as waterproof roll [7] or injecting materials that coagulate
rapidly by grouting, which requires considerable efforts and
money. And they do not always work well because locating the
leakage is not easy [8]. Nowadays, self-healing materials are
attracting plenty of attentions and have been applied in many
fields [9–12]. With self-healing ability, the number and size of
racks could be reduced, which makes concrete more durable
[13,14].
There are many approaches to achieve self-healing functionality
such as using shape memory materials [15], proper bacteria [3]
and microcapsules [13]. Unfortunately, shape memory materials
cost too much. Utilizing bacteria is not always effective in the case
of multiple damage events. Environmental problems,
especially
 G. Li et al. / Construction and Building Materials 200 (2019) 36–45
drinking water pollution, cannot be ignored when using bacteria
or microcapsules.
Neville [16] mentioned the self-healing behavior of concrete.
The general Portland concrete consists of 2CaO·SiO 2 (C 2 S),
3CaO·SiO 2 (C 3 S), 3 CaO·Al 2 O 3 (C 3 A), 4 CaO·Al 2 O 3 ·Fe 2 O 3 (C 4 AF),
SiO 2 , Al 2 O 3 , Fe 2 O 3 , MgO, SO 3 , Na 2 O, K 2 O, TiO 2 , P 2 O 5 , CaSO 4 ,
CaSO 4 ·2H 2 O, CaSO 4 ·0.5H 2 O and CaO. When water is added into
the general Portland cement, C 2 S and C 3 S hydrate then produce
CSH gel and CH. C 3 A reacts with the set retarder gypsum and water
as follows:
3CaO · Al2 O 3 þ 3ðCaSO4 · 2H 2 OÞ þ 26H 2 O
! 3CaO · Al2 O3 · 3CaSO4 · 32H2 O
ð1Þ
faceShortly
of the after mixing,
cement the[17,18].
grains formedThus
ettringite
there layer covers
is always the sur-
unreacted
cement left. On the other hand, the crystallization of calcium
car-
bonates contributes for the self-healing process [19–22]. Calcium
silicates could react with CO 2 to generate calcium carbonates and
silica gel, which blocks cracks and results in low porosity and high
density of concrete [23,24]. CH, the hydration product of cement,
provides free calcium ions that react with CO 2 to form calcium
car- bonates on both sides of cracks and fill the gaps eventually
[15]. It is believed that the formation of calcium carbonates is the
main reason for later self-healing of concrete [25]. In general, self-
healing process could be triggered by the expansion of hydrated
cementitious matrix, the formation of calcium carbonates crystals,
insoluble impurities present in water and the further hydration of
unreacted cement [26].
Considering on the above, CCCW, based on the development of
crystallization technology and thoroughly understanding of con-
crete’s chemical and physical makeup, satisfies economic and envi-
ronmental requirements at the same time. Researchers realize the
possibility to fill these cracks and capillaries to prevent the pene-
tration of water and other liquids with a chemical treatment
[26]. By diffusion, the activated chemicals in CCCW enter with
water as a migration medium and move down the capillaries or
cracks of concrete. This process facilitates the chemical reaction
between CCCW, moisture and the byproducts of cement hydration,
forming a new insoluble crystal structure. This integral structure
filling the capillary tracts endows concrete the ability of water-
resisting. CCCW shortens inspection and maintenance time by
self-healing before the leakage occurs. Meanwhile, there is no
need to worry about the environmental problems triggered by the
byproducts of bacteria or microcapsules.
Although amounts of test results have demonstrated the
advantages of CCCW, it is an agreed fact that the major compo-
nent or proportion has not been fully reported in literatures
[13,27–29]. CCCW contains cement, activated chemicals, aggre-
gate, water reducer and other additives. The self-healing ability
of CCCW could be influenced by the aggregate-cement ratio and
water-cement ratio (W/C ratio). However, it is the activated
chemicals that determine the self-healing ability of CCCW, which
means with activated chemicals, CCCW could be applied in all
cementitious circumstances to achieve an outstanding waterproof
capability despite of its components, aggregate-cement ratio or
W/C ratio.
In this research, sodium carbonate, sodium silicate,
sodium
aluminate, tetrasodium EDTA and glycine were proposed as
activated chemicals of CCCW. The second permeability and pre-
pressure self-healing tests were conducted to evaluate the self-
healing behavior and further optimize the proportion of acti-
vated chemicals of CCCW. Based on analysis of the self-healing
process by X-ray diffraction (XRD) and scanning electron
microscopy (SEM), the self-healing mechanism of CCCW was
proposed.
37
2. Experimental program and methodology
2.1. Experimental program
CCCW is a kind of rigid waterproof material used for cement
concrete. After interaction with water, the active chemicals con-
tained in CCCW penetrate the concrete by water as the carrier,
and acicular crystals insoluble in water with cement hydration
products are generated, consequently filling capillary pores and
micro-cracks, thereby improving the compactness and waterproof-
ing of concrete. In order In order to achieve the best waterproof
effect by the activated chemicals, the ratio of the active chemicals
in CCCW should be optimized.
At present, there are few evaluation criteria for self-healing per-
formance of CCCW. During the preparation process of tested
blocks, the manual insertion and ramming process and the com-
plexity of cement itself, the performance of different batches of
cement blocks might be varied, thus the tested blocks of different
groups could not be completely consistent. A simple comparison
of first and second permeability may cause serious deviation.
There- fore, appropriate adjustment of evaluation parameters is
essential. The first evaluation index was set as the ratio of second
permeabil- ity, which was the ratio between the measured value
of second permeability of CCCW and permeability of this group of
standard blocks for 14d curing periods (which is also called as the
first permeability).
Corresponding to second permeability ratio, the pre-pressure
self-healing rate is noted as another evaluation index
reflecting the self-healing ability of CCCW. The difference between
perme- ability and pre-pressure test is that the pre-pressure test
would bring relatively large cracks with irregular connectivity.
Thereby the pre-pressure self-healing rate and second
permeability ratio together serve as the evaluation index of self-
healing performance of CCCW.
Due to the particularity of concrete material itself,
impervious
tests would consume a lot of time and materials, and pre-
pressure tests would also consume a lot of time and materials.
Orthogonal experiment is a multi-factor and multi-level experi-
mental method. Through orthogonal experiments, some
represen- tative points could be selected from the overall
experiments, thus greatly reducing the workload of the
experiments [30].In this paper, orthogonal experiment is used to
optimize the activated chemicals.
Choose active chemicals basic formula of sodium carbonate,
sodium silicate, sodium aluminate, tetrasodium EDTA and glycine
as five factors obtained by previous exploratory experiment.
Among these activated chemicals, sodium carbonate, sodium sili-
cate are not easy to cause side effects, and thus their amounts
could be slightly larger. Excessive sodium aluminate would seri-
ously affect the performance of concrete. Large amount of tetra-
sodium EDTA might do harmful for the self-healing effect, and
glycine cost is relative higher. Based the above, each of the 5
active chemical factors was set four levels in the following amount
range: sodium carbonate of 0%–5.0%, sodium silicate of 1.0%–6.0%,
sodium aluminate of 1.0%–4.0%, tetrasodium EDTA of 0%–0%, and
glycine of 0–2.0%.The contents of the active chemicals are
calculated as the mass percentage of the cement, and replaced the
cement by the same amount. The orthogonal table of L16(45) was
designed, and the factor level table was shown in Table 1.
2.2. Permeability test
Each group contains six pieces of standard mortar
(70blocks
× 80 × 30 mm) prepared simultaneously with the cement con-
tent of 17.56% and the water to cement ratio of 0.6 (that is a
38 G. Li et al. / Construction and Building Materials 200 (2019) 36–45
Table 1
Factors and levels for orthogonal test.
Levels Factors
Sodium carbonate (%) Sodium silicate (%)
1 0 1.0
2 1.0 2.0
3 3.0 4.0
4 5.0 6.0
standard cement mortar proportion of P.O 42.5R ordinary Portland
cement of 330 g, ISO standard sand of 1350 g, water of 198 g and
cellulose of 0.5 g). To carry out the experiments, we coated CCCW
on four random mortar blocks each group and another two blocks
as blank samples. The CCCW with a total amount of 1.5 kg/m 2 was
coated again when the first coating film was dried to touch. After
the second coating, these specimens were moved to the standard
conservation box (Yh-40b standard constant temperature and
humidity curing box, Hebei Shuangxin testing instrument manu-
facturing co., LTD, China) curing in water under the condition of
20 °C and humidity of 90% for 14 days. With drying the surface of
the cured specimens, the side of the specimens is coated with a
melted sealing material (sealing wax) adhered to the permeable
molds. It is note that the two ends of the specimen could not apply
any sealing material. These specimens were then installed on the
permeable mortar instrument (Digital display mortar penetrome-
ter SJS-15, Shanghai meiyu instrument equipment co., LTD, China.)
as shown in Fig. 1. The water pressure of the permeable mortar
instrument was set at 0.2 MPa and hold for 2 h. Then the water
pressure was increased by 0.1 MPa per hour until the mortar
blocks leaked. The final value of water pressure minus 0.1 MPa
was marked down as the first permeability pressure of the exper-
imental group or the blank group. It is noted that the permeability
test was invalid if the permeability of blank samples is not of
0.3 MPa or 0.4 MPa. Then this group of permeable specimens was
moved to the standard conservation room soaking in water for
another 14 days with its permeable molds. The same permeability
test was proceeding again to get the second permeability of the
experimental group and the blank group. Thus the permeability
ratio can be calculated as following:
S1
SP1 ¼ × %
S0
100
S2
SP2 ¼ × 100%
S0
wherein, SP is the permeability ratio (%), S 2 , S 1 are the second and
first permeability for mortar blocks with CCCW, and S 0 is the per-
meability for blank samples.
Fig. 1. Permeability test instrument and specimen.
Sodium aluminate (%) Tetrasodium EDTA(%) Glycine (%)
1.0 0 0
2.0 1.0 0.5
3.0 2.0 1.0
4.0 3.0 2.0
2.3. Pre-pressure test
Corresponding to the permeability test, there is a pre-pressure
test. The pre-pressure test is an experiment that reflects the self-
healing ability of CCCW regarding the healing efficiency of com-
pressive strength. But too much pressure could cause large cracks
or even smashed in the concrete. Generally, concrete is a kind of
brittle material, when the ambient pressure is strong enough,
large cracks are likely to generate in normal concrete or even
broken of concrete. In this section, fiber reinforced concrete was
selected as the standard specimen for the pre-pressure
experiments. Fiber lim- its the local fracture of concrete, thus
overcoming the brittleness and low strain capacity of concrete to
a certain extent [31], result- ing in more micro-cracks [32]. These
characteristics allow fiber reinforced concrete to obtain more
reliable data in pre-pressure tests.
Some studies have pointed out [33] that when the ratio of the
received pressure load r to the maximum pressure load r 0 is
less than 0.3, there are virtually no new cracks inside the
concrete. When r / r 0 is between 0.4–0.5, new cracks are
beginning to appear and expand. When the ratio is between 0.7–
0.8, the cracks continue to spread and intersect with the
increasing pressure load. Large cracks would form when r/r0 = 0.9
and the specimen would be damaged when r/r0 = 1. Based on
this, in this pre-pressure experiments, 0.6 r 0 pressure load on
fiber reinforced concrete could give rise to micro cracks and avoid
larger cracks generated which have serious impact on
mechanical properties
In this part, of mortar.
three pieces of 40 × 40 × 160 m m fiber-
reinforced
concrete specimens were prepared according to the ISO 679-
2009 standard ‘‘Cement Test methods Determination of strength”
at the same time. The mixing proportions of the fiber-reinforced
concrete used are given in Table 2. For the fiber-reinforced con-
crete, P.O 42.5R ordinary Portland cement, sand with the average
particle size of 180 l m, 12 m m polypropylene fibers provided by
Changsha Bo Sai Te Construction Materials Co., Ltd, water reducing
agent (MELMENT ® F10) from BASF SE were used. The activated
chemicals were used to substitute the same quantity of
cement.
The 16 different proportion of activated chemicals in CCCW
numbered as E1-E16 shown in Table 3 were used to prepare the
 G. Li et al. / Construction and Building Materials 200 (2019) 36–45 39

Table 2
The Mixing proportions of the fiber-reinforced concrete (kg/m 3 ).

Materials Cem ent Aggregate Water Water reducing agent Fiber

Fiber-reinforced concrete 685 730 411 2 14

Table 3
L 1 6 (4 5 ) orthogonal array testing for permeability of CCCW.

NO. Sodium Sodium Sodium Tetra- Glycine First permeability Second permeability Second permeability
sodium carbonate silicate aluminate EDTA ratio (%)
Blank Blocks with Blank Blocks with
CCCW CCCW

E1 1 1 1 1 1 0.5 0.9 0.5 0.8 160.0

E2 1 2 2 2 2 0.3 0.6 0.3 0.8 266.7
E3 1 3 3 3 3 0.3 0.5 0.4 0.7 175.0
E4 1 4 4 4 4 0.4 0.6 0.5 0.7 140.0
E5 2 1 2 3 4 0.4 0.6 0.4 0.7 175.0
E6 2 2 1 4 3 0.3 0.9 0.3 0.9 300.0
E7 2 3 4 1 2 0.3 0.6 0.3 0.6 200.0
E8 2 4 3 2 1 0.3 0.3 0.4 0.7 175.0
E9 3 1 3 4 2 0.3 0.8 0.4 0.9 225.0
E10 3 2 4 3 1 0.3 0.6 0.3 0.7 233.3
E11 3 3 1 2 4 0.4 0.8 0.4 0.9 225.0
E12 3 4 2 1 3 0.4 0.7 0.5 0.8 160.0
E13 4 1 4 2 3 0.4 0.6 0.4 0.7 175.0
E14 4 2 3 1 4 0.3 0.6 0.3 0.7 233.3
E15 4 3 2 4 1 0.3 0.6 0.4 0.7 175.0
E16 4 4 1 3 2 0.3 0.8 0.4 0.9 225.0

specimens. The fresh fiber-reinforced concrete specimens were
demolded after 24 h and moved to the standard conservation room
curing for 28 days. After curing, the specimens were first broken
into two parts using the rupture strength tester. A random part
of each fiber-reinforced concrete specimen was chosen to conduct
the pre-pressure test. The resulted value was noted as the original
compressive strength P 0 . Then the 0.6 P 0 was pre-pressured on
another part of the specimen and held for 1 min. The pre-
pressured part was moved back to the standard conservation again
and soaking in water for 28 days. After the curing process, the
pre- pressured part was used for the pre-pressure test again to
achieve the compressive strength P 2 . The pre-pressure self-healing
rate is defined as the ratio of the compressive strength P 2 after 28
days curing to the original compressive strength correspondingly
P 0 and calculated as following:
P2
PR ¼ × 100%
P0
2.4. Characterization
XRD analysis of crystals scraped off from the cracks was carried
out on Bruker D8 ADVANCE diffractometer. The samples were
scanned from 5-to-80° (2h) using a D/max-III type automatic X-
ray diffractometer with Cu-K a radiation. The diffractometer
has a wavelength of 1.54 Å and an integrated step scan of
0.017° (2h).
Crystals scraped off from the cracks were investigated by
scanning electronic microscopy (SEM, ZEISS Merlin, Germany).
Specimens
were fixed by a conducting resin and then coated with gold
and examined by SEM at 5 kV. Optical microscope images of the
crys-
3. Results and discussion
tals were captured by 80X optical microscope (MG10085-2,
China).
3.1. Orthogonal array testing for permeability of CCCW
Herein, four levels of orthogonal test for these 5 activated
chemicals are determined in Table 1, and the orthogonal test was
carried out with the orthogonal array L 16 (4 5 ) as shown in Table 3.
16 groups of mortar blocks with CCCW, along with the correspond-
ing blank mortar blocks were prepared. The second permeability
ratio is shown in the last column of Table 3, the first and second
permeability is shown simultaneously for better understanding.
It can be seen from Table 3, the first permeability and secondary
permeability of CCCW are more than that of blank cement. How-
ever, a high first permeability groups do not correspond to the
ground with the high secondary permeability. This is because the
first permeability of CCCW is more related to the surface compact-
ness resulted from the film on the basic block, but the secondary
permeability is mainly impacted by the self-healing effect of the
block of waterproof coating on the basic block. Therefore the first
permeability and second permeability have no strict
corresponding relation. This is one reason why we choose the
second permeability ratio as a parameter for evaluating self-
healing ability of CCCW.
Based on Table 3, the influence of each activated chemical on
second permeability ratio and their preferred values could be
obtained through orthogonal analysis shown in Table 4. In the
orthogonal analysis, K1-K4 represent the corresponding second
permeability ratio at each level of activated chemicals, R denotes
the difference between the largest value and the smallest of K1-
K4. The activated chemical possessing the larger R has more signif-
icant influence on second permeability ratio. Therefore we rank
the influence order by R value that sodium silicate (83.3) > glycine
(43.5) > sodium aluminate (40.5) > sodium carbonate (27.0)
> tetrasodium EDTA (22.3).
According to Table 4, the influence of the level of activated
chemical on second permeability ratio is illustrated in Fig. 2. It
shows that through adding sodium carbonate and glycine, CCCW
possesses higher second permeability ratio. When the proportion
of sodium carbonate reaches 1.0%, or the proportion of glycine
comes to 0.5%, it has the highest second permeability ratio of
212.5% or 229.3%. When the proportion of sodium carbonate or
the proportion of glycine further increases, second permeability
ratio shows a sustained decline, but it’s higher than that one with-
out sodium carbonate or glycine even though. It verifies that
sodium carbonate and glycine be conducive to the self-healing
40 G. Li et al. / Construction and Building Materials 200 (2019) 36–45

Table 4
Analysis of orthogonal test results.

Factor Sodium carbonate Sodium silicate Sodium aluminate Tetrasodium EDTA Glycine

Second permeability ratio (%) K1 185.5 183.8 227.5 188.3 185.8

K2 212.5 258.3 194.3 210.5 229.3
K3 210.8 193.8 202.0 202.0 202.5
K4 202.0 175.0 187.0 210.0 193.3
R 27.0 83.3 40.5 22.3 43.5
260
240
Second permeability ratio
220
(%)
200
180

sodium carbonate
0
1
3
5

4
tetrasodium EDTA

glycine

0.5

2
sodium aluminate
1

6
sodium silicate

Proportion of each activated chemicals (%)

Fig. 2. Range analysis of second permeability ratio as index.

capability of concrete. However, as the activated chemicals par- the part of sodium aluminate, the second permeability ratio
tially substitute cement, the proportion of cement would shows a decrease trend generally but still rises a little at 3.0%
decrease when the proportion of activated chemicals increases. proportion of sodium aluminate. Sodium aluminate speeds up
The reduced cement is detrimental to second permeability ratio. the hardening process of concrete, in other words, under the
The second permeability ratio decreases when the increased definite water con- dition, the more sodium aluminate, the
activated chemi- cals do more harm than good. The variation smaller compactness the concrete has. It’s easier for concrete to
tendency of second permeability ratio of sodium silicate is produce macro pores or even obvious cracks when the concrete
almost the same as that of sodium carbonate and glycine. The has a worse compactness. That decreases the anti-permeability
difference is the highest sec- ond permeability ratio of 258.3% is of CCCW coating, which eventually leads to the big jump of
much higher than that of other activated chemicals. When the second permeability ratio. At 3.0% proportion of sodium
proportion of sodium silicate is the maximum, the second aluminate, it seems that the beneficial effect of the CSH gel
permeability ratio is lower than that of the blank group. The triggered by sodium aluminate keeps the anti-permeability of
second permeability ratio increases when tetra- sodium EDTA CCCW coating from dropping to some extent. As stated above,
added. It decreases when the proportion of tetra- sodium EDTA the second permeability ratio is the index for choosing the
comes to 2.0%. When the proportion comes to 3.0%, the second optimal proportion of the activated chemical. Mean- while, the
permeability ratio rises to the same value as the pro- portion of economic cost should be taken into account as well. As the
tetrasodium EDTA is 1.0%. When tetrasodium EDTA is added as an second permeability ratio is the same when the proportion of
additive, the ettringite would grow as long thick noo- dles [34]. tetrasodium EDTA is 1.0% or 3.0%, according to the economic prin-
It’s easier for CCCW to heal the cracks using more acerose ciple, it’s better to choose 1.0% of tetrasodium EDTA than
ettrigite. The reason for the decrease of second permeability ratio 3.0%. Take into account the comprehensive consideration of
at 2.0% proportion of tetrasodium EDTA is that when there are cost and performance of CCCW, the optimal proportion of
too much tetrasodium EDTA, more calcium ions would be chelated, activated chemi- cals in CCCW is as follows: sodium carbonate
which imparted the formation of ettrigite or CSH gel. Jolanta Pry- 1.0%, sodium silicate 2.0%, sodium aluminate 1.0%, tetrasodium
wer [35] showed a tendency that the higher concentration of tetra- EDTA 1.0%, glycine 0.5%. This optimal proportion of activated
sodium EDTA there is, the higher aspect ratios for calcium chemicals is not listed in the orthogonal array. It is normal that
carbonate crystals have. This explained the re-increase of second the optimal array parameter obtained is not included in
permeability ratio at 3.0% proportion of tetrasodium EDTA. For orthogonal experiments. In this case, we should still use the
optimal combination parameters to regard
 G. Li et al. / Construction and Building Materials 200 (2019) 36–45 41

a result, and cost should be considered at the same time. Perme-
ability test using the optimal proportion shows a second perme-
ability ratio of 333.3%, which is higher than all the second
permeability ratios in Table 3.
It should be emphasized that the proposed method applied is
to optimize the second permeability ratio within the given levels
shown in Table 2. If a further optimization is required, the experi-
mental procedure could be repeated within the new levels in a
minor area near the optimal second permeability ratio.
the condition of constant water-cement ratio, excessive sodium
aluminate would lead to the decrease of concrete compactness as
well as the formation of micropores or cracks more easily in the
concrete. As the proportion of sodium aluminate in E3 is of 3%,
while it’s of 2% in E15, the one with a larger proportion of sodium
aluminate has more micropores or cracks, and consequently a
lower pre-pressure self-healing rate.
3.3. X-ray diffraction analysis

For better understanding of the self-healing process of CCCW,

3.2. pre-pressure experiments
the X-ray diffraction analysis was conducted on crystals scraped
off from the cracks of blank specimens and the specimens with
Specimens for this test were prepared through the procedure
CCCW after soaking for 28 days. The samples were immersed in
mentioned in Sec. 2.3. Each group of the pre-pressure experiment
anhydrous ethanol to terminate the hydration and then dried in
was consisted of three pieces of (40 × 40 × 160) m m
an oven at 50 °C for 12 h. Different representative peaks were
specimens
prepared in the meantime. The pre-pressure self-healing test was
shown in Fig. 4. Herein, the activated chemicals of CCCW are
performed on each specimen. Each group of the pre-pressure
sodium carbonate 1.0%, sodium silicate 2.0%, sodium aluminate
experiments would carry out 3 times and the average pre-
1.0%, tetrasodium EDTA 1.0% and glycine 0.5%. The standard
pressure self-healing rate was obtained and shown in Fig. 3.
cement mortar with the cement content of 17.56% and the water
As can be observed in Fig. 3, even the lowest pre-pressure self-
to cement ratio of 0.6 were prepared with or without activated
healing rate of E1-E16 (103.1%) is higher than that of the blank
chemicals.
group (87.3%). The pre-pressure self-healing rate test considers
It can be seen from Fig. 4 that the main component of the crys-
CCCW as the whole part rather than considering CCCW just as a
tals scraped off from the specimens with CCCW is the same as
coating covering blocks for permeability test. Higher pre-pressure
those of the blank specimen. Peaks at 29.64, 32.32, 49.97 are
self-healing rate means the better self-healing ability. Comparing
related to CSH and peaks at 18.20, 34.27, 47.27, 50.94 are related
to second permeability ratio in Table 3, higher pre-pressure self-
to CH are shown in XRD patterns. From the XRD patterns of the
healing rate corresponds to higher second permeability ratio. How-
crystals from the specimens with CCCW, the intensities of the
ever, the pre-pressure self-healing rate and second permeability
peaks characterizing CSH increase and meanwhile the
ratio are not corresponded strictly. For example, E1 has a higher
intensities of the peaks charactering CH decrease comparing to
pre-pressure self-healing rate while E3 has a higher second perme-
the blank specimen. This attributed to the consumption of CH
ability ratio, that’s contribute to the total proportion of the acti-
caused by the addition of CCCW. CCCW reacted with CH and thus
vated chemicals. In this experiment the activated chemicals
lead to more CSH generation, which participated in pores and
substitute cement partially, the higher proportion of the activated
cracks dur- ing the curing process. This is also associated with the
chemicals in CCCW means less cement in CCCW. The Less cement
higher pre- pressure self-healing rate of the specimen with CCCW
is harmful to the compressive strength of CCCW and meanwhile
than that of the blank group.
limits the self-healing ability relatively. Meanwhile, there are also
some groups like E3 and E15 with the identical second
permeabil- ity ratio in the permeability test but have different 3.4. Scanning electron microscopy
pre-pressure self-healing rates in pre-pressure self-healing test. In
terms of total proportion of the activated chemicals, E3 has a total Specimens for SEM were prepared by the same procedure of the
proportion of the activated chemicals of 13% while E15 has of 14%. specimens for XRD analysis. Fig. 5 shows SEM images of crystals
We conclude that the difference between the total proportions of from cracks of cementitious mortar blocks without and with
the activated chemicals is not the major cause leads to the CCCW after soaking for 28 days. Herein, the activated chemicals of
different pre- pressure self-healing rates. The main reason is the CCCW are sodium carbonate 1.0%, sodium silicate 2.0%, sodium
different pro- portion of sodium aluminate. As the above analysis, aluminate 1.0%, tetrasodium EDTA 1.0% and glycine 0.5%. The
sodium alumi- nate can promote the hydration of unhydrated standard
cement, but under
Blank
180 CCCW
CSH
160
Calcium carbonate
Pre-pressure self-healing rate, %

140 CH

120
CPS

100

80

60

40

20
10 20 30 40 50 60 70 80
0
Blank E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14 E15 E16 2 °

Fig. 3. The pre-pressure self-healing rate of E1-E16 and the blank group. Fig. 4. X R D analysis of crystals from blank specimen and the specimens with C C C W.
42 G. Li et al. / Construction and Building Materials 200 (2019) 36–45

Fig. 5. S E M of crystals from cracks of specimens: a) blank specimen; b) ~ e) specimens with C C C W.

cement mortar with the cement content of 17.56% and the water
to cement ratio of 0.6 were prepared with or without activated
chemicals.
As shown in Fig. 5, lots of CSH are generated in specimens with
CCCW comparing to the blank specimen. There are also less CH
and more ettringite in specimens with CCCW, which is helpful for
the compactness and self-healing ability of concrete.
3.5. Visual assessment of self-healing behavior
Specimens with CCCW were pre-cracked at the age of 28 days
and then immersed into water soaking for another 28 days. It can
be seen clearly that the cracks were healed and covered by white
precipitates in Fig. 6. When cracks were healed by white crystals,
water could not penetrate through origin cracks as expected.

Fig. 6. Cracks of specimens with C C C W after self-healing.

 G. Li et al. / Construction and Building Materials 200 (2019) 36–45 43

Herein, the activated chemicals of CCCW are sodium carbonate
1.0%, sodium silicate 2.0%, sodium aluminate 1.0%, tetrasodium
EDTA 1.0% and glycine 0.5%. The standard cement mortar with
the cement content of 17.56% and the water to cement ratio of
0.6 were prepared with or without activated chemicals.
In order to obverse the crystals directly, the pre-cracked speci-
mens with CCCW through 28 days soaking into water were
tested. For comparison, the pre-cracked specimens without CCCW
with the same conditions were also tested. There are not any
white crys- tals presented on the surface of specimen from Fig. 7a.
But from Fig. 7b, there are numerous of large visible white
crystals gener- ated. These crystals are attached on the fracture
surface and play an important role in healing process. For
further investigate the
state of crystals generated on the specimens with CCCW, we dry
the wetted specimens with white crystals under room tempera-
ture. The crystals are still attached to the fracture surface as well
under the dried condition in Fig. 7c. It verifies that these numerous
crystals fill full of the cracks and thus the cracks are blocking to
accomplish the self-healing process.
Furthermore, Fig. 7d shows the fiber-reinforced specimens with
CCCW after 28 days curing. There are large amount of white crys-
tals attached to fibers clearly on the fracture surface. 80X optical
microscope was used to observe the crystals attached to fibers in
Fig. 8. The crystals with an average diameter of 0.2 m m and
not any crystals with very large diameter presented. These crystals
stack together for blocking cracks, and thus display the self-
healing

Fig. 7. Images of fracture surface of specimens: a) blank; b) wetted; c) dried; and d) with fiber-reinforced.

Fig. 8. 8 0 X optical microscope images of the crystals attached to fibers.

44 G. Li et al. / Construction and Building Materials 200 (2019) 36–45
Fig. 9. 8 0 X optical microscope images of cracks: a) before healing; b) after healing.
ability of CCCW. It is worth that the average diameter of 0.2 m m
agrees well with the fact that CCCW works effectively only when
crack width is no more than 0.4 m m generally. If cracks are too
wide, it’s hard for these crystals to stack compacted to block
cracks and easily to be washed away by permeated water.
For better understanding of self-healing ability of CCCW, 80X
optical microscope was used to observe the cracks of the fiber-
reinforced specimens with CCCW before and after self-healing in
Fig. 9.
It can be seen from Fig. 9a that there are origin cracks of 0.2 m m
wide. Fig. 9b shows that the cracks are healed after the self-
healing process. White crystals are generated and the crystals
stacked together and consequently sealed the cracks. With the
generation of numerous crystals on both sides of cracks, the self-
healing behavior of CCCW is achieved.
3.6. Self-healing mechanism analysis
As we know that, activated chemicals of CCCW are soluble in
water. The capillary pore structure in the concrete structure makes
it easy for water to permeate, but simultaneously it also gives the
condition for the active chemicals of CCCW to permeate into the
concrete [36].
Sodium carbonate is one kind of pH buffer. If the cementitious
material cracked, acid rain is easy to permeate into the
interior
of concrete and even corrode the steel bars. Sodium
carbonate reacts with the acid rain to maintain the alkaline
environment of
cement, which is essential for the protection of steel bars and
the durability of concrete. What’s more, when CH dissolved in
water
partially, the carbonate ions penetrate into the interior of
concrete with the penetrated water and react with sodium
carbonate. The
osmotic pressure caused by the calcium ion concentration
differ- ence between inside and outside of the concrete also
helps the
This reaction could generate dense precipitation of calcium car-
penetration of carbonate ions. Sodium carbonate reacts with
bonate and consume CH, as shown in Fig. 3. The solubility of CH
the hydration product CH as follows:
makes it a threat for the compactness of concrete. In the
meantime, byproduct sodium hydroxide could maintain the
Na2 CO3 þ CaðOHÞ2 ! CaCO3 # þ2NaOH
alkalinity of the concrete and accelerate the hardening of
ð2Þ
cement.
Sodium
react with silicate dissolves
the calcium ionsin and
water easily. Dissolved
generate CSH gel silicate
to heal ions
the
cracks. From Figs. 1 and 4, it can be seen that the reaction of
calcium ions with the sodium silicate plays an important role in
the self-healing process.
Sodium aluminate helps generate ettringite and sodium
hydroxide in cement. Sodium hydroxide speeds up the absorption
of carbon dioxide to form carbonate ion thus accelerates the for-
mation of calcium carbonate. The hydrolysis reaction of sodium
aluminate and the reactions that generate ettringite are as follows:
NaAlO 2 þ 2H2 O ! AlðOHÞ 3 þ ð3
NaOH Þ
2NaAlO2 þ 3CaO þ 7H 2 O ! 3CaO · Al2 O 3 · 6H 2 O þ
2NaOH ð4
Þ
3CaO · Al2 O 3 · 6H 2 O þ 3ðCaSO4 · 2H 2 OÞ þ 20H2 O ð5
! 3CaO · Al2 O 3 · 3CaSO4 · 32H 2 O Þ
Tetrasodium EDTA, as one of the calcium chelators, attaches to
the calcium carbonate crystal and decreases its interfacial energy,
which changes the crystal shape of calcium carbonate [37]. When
Tetrasodium EDTA added, calcium carbonate grows as long thick
noodles according to AM Cody [34]. Calcium carbonate crystals
with higher aspect ratios could block the cracks more efficiently.
Glycine is a corrosion inhibitor of steel bars. When CCCW faced
with water, there are plenty of calcium ions in the system. Glycine
and rich calcium ions chelates to generate calcium glycine, thus
plays an important role in calcium ions accumulation. When the
hardened concrete is cracked, there is CH on both sides of cracks.
However, calcium ions provided by the solution of CH are not
enough for the self-healing process. When water permeated into
the interior of concrete, calcium glycine dissolves in the relatively
restricted space and releases a part of calcium ions. This enhances
the concentration of calcium ions and thus accelerates the process
of the combination of calcium ions and silicate ions in concrete.
When the self-healing process finished, there would be a little
amount of water at the original cracks. The released glycine che-
lates with calcium ions dissolved from CH to form calcium glycine,
which is prepared for the next self-healing process and consume
CH beforehand. Besides, when water is permeated deep enough
to reach the steel bars, calcium glycine could convert to ferrous
bis- glycinate due to the calcium glycine is more unstable. Ferrous
bis- glycinate attached to the steel bars slows down the corrosion
process of steel bars while the released calcium ions participate
in the self-healing process continuously.
4. Conclusions
This research focuses on the components and proportions of
activated chemicals of CCCW instead of its aggregate ratio or
W/C ratio to obtain the optimal self-healing capability. The second
permeability ratio and pre-pressure self-healing rate as two key
evaluation indexes were carried out. The optimal proportion of
 G. Li et al. / Construction and Building Materials 200 (2019) 36–45
the activated chemicals of CCCW is as follows: sodium carbonate
1.0%, sodium silicate 2.0%, sodium aluminate 1.0%, tetrasodium
EDTA 1.0%, and glycine 0.5%. Sodium silicate has the most signifi-
cant impact on the self-healing ability of CCCW. The activated
chemicals of CCCW show good self-healing ability both on second
permeability ratio and pre-pressure self-healing rate comparing
to the blank specimens. The consumption of CH and the formation
of CSH gel, calcium carbonate and ettringite were observed by
means of XRD and SEM. The formation of CSH gel, calcium
carbonate and ettringite improve the compactness and self-
healing ability of cementitious materials. The CCCW with
activated chemicals gener- ate white crystals with an average
diameter of 0.2 m m and seal the cracks through the accumulation
of white crystals. Based on the XRD and SEM analysis, the
combined action of the dissolution of CH, generation of CSH gel
and ettringite, maintenance of the alka- line environment of
cement, adsorption of carbon dioxide, acceler- ation of the
generation of calcium carbonate, enrichment of calcium ions by
the complexing agent, complexing-precipitation that accelerating
the generation of calcium silicate precipitation as well as
acceleration of hydration of unhydrated cement particles
promoting the self-healing behavior of CCCW was proposed.
Conflict of interest
None.
Acknowledgements
The authors would like to acknowledge the financial support
of Science and Technology Planning Project of Guangdong
Province, China (2015A010105008) and the National Natural
Science Foundation of China (51576070), China.
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