Construction and Building Materials 297 (2021) 123822

Contents lists available at ScienceDirect

Construction and Building Materials

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

The features of different mineral admixtures affecting the self-healing

capacity of cementitious-based materials
Honglei Chang a, Chencong Li a, Jianhong Wang a, Hongzhi Zhang a, Zhi Ge a, Zhiwu Zuo b, Jian Liu a,⇑,
Yang Zhou c,⇑
a
School of Qilu Transportation, Shandong University, Jinan 250002, China
b
Shandong Hi-Speed Group Co., Ltd, Jinan 250098, China
c
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China

h i g h l i g h t s

Self-healing performance of mortars blended with mineral admixtures are evaluated.

Influence of admixture type, crack age, and crack width on healing effect are analyzed.

Relationship between crack healing degree and water permeability is established.

Composition and micromorphology of healing products in cracks are detected.

Mechanism of mineral admixtures influencing the self-healing capacity is revealed.

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

Article history: Using mineral admixtures to improve the self-healing capacity of cementitious-based materials is a valid
Received 12 January 2021 and economical method. To achieve a better understanding of the characteristics of different mineral
Received in revised form 24 March 2021 admixtures affecting the self-healing performance of matrix, this study evaluated the self-healing capac-
Accepted 29 May 2021
ity of mortar specimens blended with different kinds of mineral admixtures through testing crack width
and water permeability, and characterized the healing products in cracks with microanalysis tools. The
results show that, with the increase of healing time, the healing degree of cracks increases while water
Keywords:
permeability of specimens decreases, presenting a linear correlation. Moreover, as for improving the self-
Mineral admixture
Self-healing
healing capacity of matrix, slag (SL) only works at age 28d; fly ash (FA) mainly functions after 28d; meta-
Crack kaolin (MK) and limestone (LS) are extraordinary within 28d, especially LS, its effect within 28d is the
Water permeability most significant; and silica fume (SF) works well in the whole 112d age. Furthermore, calcium silicate
Healing product hydrate gel (C-S-H) and calcium carbonate (CaCO3) are the two major healing products, supplemented
by some Al-contained compounds and Mg-contained compounds, which is closely related to the chemical
composition of mineral admixtures. Therefore, to better improve the self-healing capacity of
cementitious-based materials, it is suggested to come up with a rational and optimized mineral admix-
ture composition based on the feature of every mineral admixture.
Ó 2021 Elsevier Ltd. All rights reserved.

1. Introduction tates the penetration of external moisture and corrosive ions to

Concrete is a quasi-brittle composite cementitious material that
easily fractures under tensile loading. The resulted micro-fractures
(<0.4 mm) themselves have negligible impact on the safety of con-
crete structures since they have been taken into consideration at
initial designing [1]. However, the presence of those cracks facili-
⇑ Corresponding authors.
E-mail addresses: lj75@sdu.edu.cn (J. Liu), tomasy@seu.edu.cn (Y. Zhou).
the steel bars in concrete, increases the odds of steel corrosion,
and leads to the failure of concrete structures. Therefore, the exis-
tence of micro-fractures is a great potential hazard, which can not
be ignored.
To solve the above mentioned problems caused by micro-
cracks, self-healing of concrete can be an effective solution except
for externally applied repair methods [2]. The healing process in
concrete can be classified broadly into autonomic healing and
autogenous healing [3,4]. The former is mainly through employing
microcapsules or hollow glass tubes that contain healing adhesives

https://doi.org/10.1016/j.conbuildmat.2021.123822
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
H. Chang, C. Li, J. Wang et al.
[5,6] or bacteria [7]. And cracks can be partially repaired by the
those encapsulated healing agents released by breaking the encap-
sulation (hollow glass fibers [8,9] or microcapsule [10,11]). The lat-
ter is currently based on the inherent healing capacity of
cementitious materials, e.g. further hydration or swelling of unre-
acted particles [12]. Those particles can be cement as well as other
supplementary cementitious materials, which have not been fully
hydrated in the initial stage of hydration [13].
Compared with autonomic healing, autogenous healing is cost-
effective in terms of the current economy scale and application
market. According to the cost analysis of different healing tech-
niques in cementitious materials made by Huang [14], the price
of self-healing concrete based on mineral admixtures (autogenous
healing) is not higher than that of traditional concrete. Whereas,
the cost of other methods, like encapsulation techniques and bac-
teria methods, is much higher at present. But the price may drop if
encapsulations is widely used. Besides, careful operations are
required for autonomic healing method. For instance, the imple-
mented microvascular glass tube probably makes the casting of
concrete difficult and may weaken the mechanical response of
the host matrix because they are comparably less rigid than con-
crete. Therefore, though those autonomic healing techniques can
produce the desired results, the cost and operability will limit their
application in practical engineering. On the contrary, the autoge-
nous healing method based on mineral admixtures is more
applicable.
So far, plenty of studies have be conducted on autogenous heal-
ing based on mineral admixtures, and various alternative cementi-
tious materials, such as fly ash (FA), blast-furnace slag (SL), silica
fumes (SF), limestone (LS), bentonite clay (CL), etc. have been used.
Qureshi [4,15] systemically reviewed the relevant studies, and
found that the hydration of un-hydrated cement and expansive
minerals initiated the recovery of strength, sealing of cracks, and
reduction of permeability. Meanwhile, the recovery and crack seal-
ing efficiency of cement mixes containing expansive minerals was
significantly increased compared with that of pure cement. Zhou
[16] studied the influence of FA and SL on the self-healing ability
of concrete, and the results showed that optimum healing perfor-
mance could be obtained when the dosage of FA and SL was 40%
and 30% respectively. Moreover, Tittelboom [17] compared the
self-healing effect of cementitious materials blended with SL, FA
and LS, and discovered that LS containing mix showed good heal-
ing performance, but the SL and FA showed negative influence on
sealing efficiency at a given dosage. Similar to the results of Tittel-
boom, Olivier [18] found that 100% PC samples showed better self-
healing performance than slag PC mix in the early healing period.
However, this performance deteriorates in the case of PC with
50% SL samples. Furthermore, mineral admixtures such as FA, SF,
and crystalline additives were investigated by Jaroenratanapirom
[19] for improving the self-healing of specimens. It was found that
micro-cracks up to 50 lm were completely healed within 12 days,
and some cracks healed better when SF was mixed. The results of
Qian [20] showed that cracks (60 lm) in SL and LS containing
fiber-reinforced cementitious composites healed efficiently. Actu-
ally, for autogenous healing, there is a maximum allowable crack
width (about 400 lm) at a given mineral admixture content and
curing condition, beyond which cracks cannot be healed com-
pletely [21–23]. Furthermore, the experiment results of Jiang [24]
showed that early appeared cracks healed more efficiently when
they were cured in still rather than flowing water and the healing
efficiency can be further improved by mixing multiple mineral
materials (silica fume, bentonite, sodium carbonate etc.) rather
than a single mineral. The study of Sisomphon [13] indicated that
the mixtures with expansive additive (CSA) and crystalline addi-
tive (CA) showed favorable surface crack closing ability. In addi-
tion, Huang [25] investigated the physical–chemical process of
2
Construction and Building Materials 297 (2021) 123822
self-healing in cement paste with high dosage of slag and saturated
Ca(OH)2 solution as activator. It was found that high dosage of slag
had superior healing effect and the healing rate was faster in the
first 50 h.
Based on above, autogenous healing based on mineral admix-
tures has a positive effect on improving the self-healing perfor-
mance in general. Therefore, considering the superior healing
effect and price advantage, the application of autogenous healing
method is feasible. However, compared with pure cement, the
use of mineral admixtures may not necessarily improve the self-
healing ability of matrix at certain cracking ages. Besides, the char-
acteristics of different mineral admixtures affecting the self-
healing ability of the matrix have not been accurately mastered
yet. For example, FA may strengthen the self-healing capacity of
matrix at the age of 28d, but whether FA still has the same
improvement effect on specimens at 3d, 7d, or 112d is uncertain.
Such a situation is also true for other mineral admixtures. Thus,
more investigations are needed to evaluate the self-healing fea-
tures of specimens blended with mineral admixtures at different
cracking ages and in a prolonged duration.
This study evaluated the self-healing performance of six types
of mortar specimens (involving cement and five kinds of mineral
admixtures) at different cracking ages through monitoring and
testing crack width and water permeability, and thereby, the
impact of healing time, cracking age, and initial crack width on
self-healing effect of matrix were explored. Meanwhile, the self-
healing features of different specimens at different crack ages were
analyzed and compared to provide a reference for the rational use
of each kind of mineral admixtures. Moreover, the composition and
micromorphology of healing products in cracks were detected with
X-ray diffraction (XRD) and scanning electron microscope and
energy-dispersive X-ray spectroscopy (SEM-EDS) to reveal the
mechanisms of mineral admixtures influencing the self-healing
capacity of matrix.
2. Experiments
2.1. Raw materials
Ordinary Portland Cement 42.5 and five kinds of mineral
admixtures (fly ash, FA; slag, SL; silica fume, SF; Metakaolin, MK;
limestone, LS) were used. And the fineness of FA, SL, SF, MK, and
LS is 615 m2/kg, 384 m2/kg, 17430 m2/kg, 827 m2/kg, and
305 m2/kg respectively. The chemical composition of cement and
mineral admixtures is shown in Table 1. In addition, well-graded
river sand with fineness modulus of 2.3 was used to cast mortar
specimens.
2.2. Mix proportions
The mix proportions of mortar specimens are shown in Table 2.
The proportion of FA, SL, SF, MK, and LS replacing cement is 30%,
30%, 10%, 10%, and 10% separately, replacing cement by mass.
The dosage of every mineral admixture was designed referring to
its common dosage in cement-based materials [4,15–17]. Besides,
water-to-binder ratio (w/b) of 0.45 and sand-to-binder mass ratio
(s/b) of 2.0 were used.
2.3. Sample preparation
The mortar specimens are cylinders of size Ø100
mm  200 mm. During casting, partial paste was first filled in
the mould, and after adjusting its content the upper surface was
managed to reach the 15 mm scale (measured from the bottom).
Then, a stainless steel mesh with diameter slightly smaller than
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

Table 1
The chemical composition of cement and mineral admixtures (%).

Chemical composition (%) SiO2 Al2O3 Fe2O3 CaO MgO TiO2 Na2O K2O SO3
Cement 21.1 7.8 2.9 54.4 3.2 0.4 0.2 0.4 2.9
FA 49.9 31.7 6.7 4.5 0.7 1.4 0.4 2.4 0.6
SL 30.0 14.6 0. 6 39.4 8.7 1.8 0.5 0.5 2.5
SF 95.7 0.8 0.9 0.3 0.7 0.0 0.2 0.6 0.7
MK 49.0 46.9 0.6 0.2 0.3 1.5 0.2 0.2 0.3
LS 3.5 1.2 0.8 87.9 4.8 0.8 0.2 0.3 0.5

Table 2
Mix design of mortars by mass ratio (%).

Mix OPC FA SL SF MK LSA Water Sand

M1-CM 100 – – – – – 45 200
M2-FA30 70 30 – – – – 45 200
M3-SL30 70 – 30 – – – 45 200
M4-SF10 90 – – 10 – – 45 200
M5-MK10 90 – – – 10 – 45 200
M6-LS10 90 – – – – 10 45 200

100 mm was placed on the paste surface, and then pasted was
filled in again, vibrated and adjusted content, followed by a stain-
less steel mesh. The cycle was repeated several times, at the scale
of 47 mm, 79 mm, 111 mm, 143 mm, and 175 mm successively. In
the end, the remaining space of mould was filled with paste and
then compacted through vibrating. Illustration of the location of
stainless steel mesh in cylinder specimen is shown in Fig. 1(a).
The surface of mould was sealed with a plastic film to prevent
moisture evaporation, and then all specimens were placed in a
room of 23 ± 2 ℃ temperature for 24 h.
Specimens were demolded after 24 h, and cured in a room of
23 ± 2 ℃ temperature and higher than 90% humidity. At the age
of 3d, specimens were taken out, and each was cut into six
Ø100mm  30 mm samples with a precision cutting machine.
2 mm thickness of cutting loss was pre-prepared between every
two batch layers during casing to guarantee that every stainless
steel mesh is located in the middle of each specimen of 30 mm
thickness, shown in Fig. 1(b). Furthermore, four preferable speci-
mens were chosen from the six ones to be cured to the age of 3d,
7d, 28d, and 112d (Note that these ages are also named crack ages
in this study, meaning that specimens will be cracked at that age.),
labeled M1-CM-3d, M1-CM-7d, M1-CM-28d, and M1-CM-112d
separately (taking M1-CM as an instance).
2.4. Manufacturing cracks
After specimens reached corresponding ages, multi-function
press machine was used to produce a longitudinal crack with
<0.5 mm width under the loading rate of 0.1 mm/s, shown in
Fig. 2. With the constraint provided by the stainless steel mesh,
specimens wouldn’t split for overloading during pressure exertion.
2.5. Crack width
After the crack was ready, 5 points were marked along the
crack, shown in Fig. 3. The crack width at the marked points should
be preferably within 0.20 ~ 0.40 mm. Then, the exact initial crack
width at those 5 points (the distance interval between every two
points is about 10 mm) were measured with an industrial electron
microscope of 0.1 lm precision. Next, specimens were immersed
in tap water under temperature of 23 ± 2 ℃, and then taken out
for crack width test after 3d, 7d, 14d, 28d, 56d, and 112d succes-
sively. Note that specimens of each mix were placed in separate
container to avoid mutual interference, and the curing water was
replaced every week.
As the initial crack width differs from each other, it is hard to
compare the self-healing performance of different specimens.
Thus, the healing degree was proposed to represent the healing
efficiency of cracks.
 
di
D¼ 1  100% ð1Þ
d0

Where, D is the healing degree of cracks; d0 is initial crack width; di

is the width of the same crack with a healing time of i days.

2.6. Water permeability

The water permeability of specimens were measured using a

constant water head method, which has been widely employed
in many studies [13,26–28]. The schematic diagram of water pass-
ing test is shown in Fig. 4. A glass tube with inner diameter of
75 mm and height of 220 mm was prepared and marked at the
height of 200 mm. The glass tube was fixed to the specimen using
fast hardening adhesive, making sure that water cannot escape
from the interface between them. Then, water was added in the
(a) Before cutting (b) After cutting tube until reaching the 200 mm mark. The water head was
remained constant at 200 mm during the test. The exuded water
Fig. 1. Illustration of the location of stainless steel mesh in cylinder specimen. content in 5 min, starting from water oozing out specimens, was
3
H. Chang, C. Li, J. Wang et al.
Fig. 2. Crack manufacturing process.
Fig. 3. Crack width testing.
Fig. 4. The schematic diagram of water passing test.
recorded, and the water passing rate was calculated with Eq. (2).
Thus, the water passing rate of samples healed for 0d, 3d, 7d,
14d, 28d, 56d, and 112d can be obtained. Note that specimens
for water permeability test are the same specimens for crack width
test. After reaching curing age, the crack width of specimens was
first measured and then the water passing rate was tested. In addi-
tion, to avoid the influence of water absorbed by the specimen
itself on the accuracy of water permeability, specimens with the
prefabricated crack were firstly saturated with water in a vacuum
tank, and then cured in water.
VL
W¼
Aht
Construction and Building Materials 297 (2021) 123822
Where, W is the water passing rate of specimens; V is the volume of
liquid passing through specimens during the test; L is the specimen
thickness in the direction of water flow; A is the cross-sectional area
subjected to water flow; h is the constant water head; and t is the
testing time.
The difference in the initial width of cracks may lead to the dif-
ference in the consequent permeability. Thus, relative water pass-
ing rate was obtained through Eq. (3) to better illustrate self-
healing performance from the view of water permeability.
Wi
RW ¼ ð3Þ
W0
Where, RW is the relative water passing rate of specimens; W0 and
Wi are the water passing rate of cracked mortars initially and after
certain healing time, separately.
2.7. Xrd
As shown in Fig. 5, specimens of 3d crack age were split along
the crack direction after healed for 112d. Powder samples were
extracted from crack planes using the rotary tool with steel brush
attachment, and sifted through an 80 lm sieve. Then, powder sam-
ples were dried in a 45 ℃ vacuum oven for 7d. Afterwards, the
phase composition of healing products was detected using XRD.
Bruker 08 Advance X-ray diffractometer was used, and the scan-
ning region was between 2h values of 10° to 70°, at a rate of
0.03°/step.
2.8. SEm-EDS
Specimens of 3d crack age were split after healed for 112d, and
lumpy samples of 3.0–5.0 mm were taken from the crack surface
with tools, shown in Fig. 6. Those samples were immersed in abso-
lute ethyl alcohol for 3d to stop hydration. Then, samples were
ð2Þ dried in a 45 °C vacuum oven for 7d and then sprayed with gold
to make them conductive. Finally, SEM-EDS was conducted to
4
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

Fig. 5. Preparation of samples used for XRD test.

Fig. 6. Preparation of samples used for SEM-EDS test.

100 100
Healing degree/%

Healing degree/%
P1: 0.311mm
75 P2: 0.360mm 75
P3: 0.334mm
P4: 0.302mm
P5: 0.369mm P1: 0.315mm
50 50
ACW=0.335mm P2: 0.329mm
STD=0.029 P3: 0.372mm
25 P4: 0.370mm
25
P5: 0.320mm
ACW=0.341mm
STD=0.028
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(a) 3d (b) 7d

P1: 0.356mm
P1: 0.267mm 100
100 P2: 0.285mm
P2: 0.306mm
P3: 0.359mm
Healing degree/%

P3: 0.301mm
Healing degree/%

P4: 0.369mm
P4: 0.269mm 75 P5: 0.366mm
75 P5: 0.309mm
ACW=0.351mm
ACW=0.286mm
STD=0.026
STD=0.019 50
50

25
25

0
0 0 14 28 42 56 70 84 98 112
0 14 28 42 56 70 84 98 112 Healing time/d
Healing time/d
(c) 28d (d) 112d

Fig. 7. The healing degree of cracks in M1-CM at different crack ages (ACW = average initial crack width, STD = standard deviation of initial crack width).

study the microscopic morphology and elementary composition of
healing products in cracks using Quanta 250 at an accelerating
voltage of 20 kV and current of 20 mA.
3. Results and discussion
3.1. Self-healing degree of cracks
The crack healing degrees of different specimens are presented
in Figs. 7–12. It is clear that the healing degree of cracks increases
with healing time regardless of mineral admixture type, crack age,
or initial crack width. Such healing is caused by the self-healing
capacity of cementitious-based materials themselves, that is, the
generation and accumulation of new substances produced by the
hydration of cement and mineral admixtures [12–14,24]. Besides,
the increase of healing degree declines generally with healing time
growing. That is because, on the one hand, the hydration effect
weakens with time increasing, leading to the decrease of healing
products, and on the other hand, the healing substances produced
on crack surface not only fill in cracks but also impede the penetra-
tion of external liquid or gas that facilitates the generation of heal-
ing materials, which probably hinders the further healing of cracks.

5
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

P1: 0.397mm
100
100 P2: 0.323mm
P3: 0.315mm

Healing degree/%
Healing degree/%
P1: 0.183mm P4: 0.266mm
P2: 0.317mm
75 P5: 0.221mm
75
P3: 0.263mm ACW=0.304mm
P4: 0.088mm STD=0.066
P5: 0.169mm 50
50
ACW=0.204mm
STD=0.089
25
25

0
0 0 14 28 42 56 70 84 98 112
0 14 28 42 56 70 84 98 112 Healing time/d
Healing time/d
(a) 3d (b) 7d

P1: 0.339mm
100 100 P2: 0.253mm
P3: 0.205mm
Healing degree/%

Healing degree/%
P4: 0.228mm
75 75 P5: 0.191mm
ACW=0.243mm
STD=0.058
50 50

P1: 0.255mm
25 P2: 0.343mm 25
P3: 0.392mm
ACW=0.344mm P4: 0.369mm
STD=0.053 P5: 0.359mm
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(c) 28d (d) 112d
Fig. 8. The healing degree of cracks in M2-FA30 at different crack ages.

100 100
Healing degree/%

Healing degree/%

75 P1: 0.326mm 75
P2: 0.398mm
P3: 0.399mm
50 P4: 0.392mm 50 P1: 0.335mm
P5: 0.376mm P2: 0.339mm
P3: 0.318mm
ACW=0.378mm P4: 0.255mm
25 STD=0.031 25
P5: 0.384mm
ACW=0.338mm
STD=0.057
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(a) 3d (b) 7d

P1: 0.323mm
100 100
P2: 0.339mm
Healing degree/%

P3: 0.361mm
Healing degree/%

P4: 0.399mm
75 75 P5: 0.355mm
ACW=0.355mm
STD=0.029
50 50
P1: 0.317mm
P2: 0.382mm
25 P3: 0.323mm 25
ACW=0.324mm P4: 0.341mm
STD=0.046 P5: 0.256mm
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(c) 28d (d) 112d

Fig. 9. The healing degree of cracks in M3-SL30 at different crack ages.

6
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

100 100
P1: 0.384mm

Healing degree/%

Healing degree/%
P2: 0.314mm
75 P3: 0.394mm 75 P1: 0.212mm
P4: 0.395mm
P5: 0.376mm P2: 0.344mm
P3: 0.249mm
50 ACW=0.373mm 50 P4: 0.276mm
STD=0.034
P5: 0.201mm
ACW=0.256mm
25 25 STD=0.057

0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d

(a) 3d (b) 7d

P1: 0.337mm
100 100 P2: 0.372mm
P3: 0.335mm

Healing degree/%
Healing degree/%

ACW=0.315mm P4: 0.281mm

75 75 STD=0.049 P5: 0.249mm

50 P1: 0.262mm 50
P2: 0.317mm
P3: 0.382mm
25 P4: 0.366mm 25
P5: 0.231mm
ACW=0.312mm
STD=0.065
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(c) 28d (d) 112d

Fig. 10. The healing degree of cracks in M4-SF10 at different crack ages.

100
P1: 0.363mm 100
Healing degree/%

P2: 0.346mm P1: 0.351mm

Healing degree/%

75 P3: 0.209mm P2: 0.385mm

P4: 0.308mm 75 P3: 0.399mm
P5: 0.244mm P4: 0.312mm
ACW=0.294mm
50 P5: 0.284mm
STD=0.066 50 ACW=0.346mm
STD=0.048
25
25

0
0 14 28 42 56 70 84 98 112 0
Healing time/d 0 14 28 42 56 70 84 98 112
Healing time/d

(a) 3d (b) 7d

P1: 0.350mm
100 100
P2: 0.363mm
Healing degree/%

P3: 0.322mm
Healing degree/%

P4: 0.345mm
75 75 P5: 0.393mm
ACW=0.355mm
P1: 0.326mm STD=0.026
50 P2: 0.392mm 50
P3: 0.379mm
P4: 0.357mm
25 P5: 0.292mm 25
ACW=0.349mm
STD=0.041
0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(c) 28d (d) 112d

Fig. 11. The healing degree of cracks in M5-MK10 at different crack ages.

7
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

100 100
P1: 0.360mm P1: 0.356mm

Healing degree/%

Healing degree/%
P2: 0.348mm P2: 0.373mm
75 P3: 0.344mm 75 P3: 0.332mm
P4: 0.329mm P4: 0.270mm
P5: 0.313mm P5: 0.312mm
50 ACW=0.339mm 50
ACW=0.329mm
STD=0.018 STD=0.040

25 25

0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d
(a) 3d (b) 7d

100 100 P1: 0.254mm

P2: 0.349mm
Healing degree/%

P3: 0.361mm

Healing degree/%
P4: 0.329mm
75 75 P5: 0.313mm
P1: 0.384mm
ACW=0.321mm
P2: 0.395mm
STD=0.042
50 P3: 0.246mm 50
P4: 0.323mm
P5: 0.278mm
25 ACW=0.325mm 25
STD=0.065

0 0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d

(c) 28d (d) 112d

Fig. 12. The healing degree of cracks in M6-LS10 at different crack ages.

From Fig. 7, it can be seen that pure cement specimens also pos-
sess the capacity of self-healing. Especially when the crack age is
3d (Fig. 7(a)), the crack of specimens can be 80% healed after cured
for 7d, and completely healed after 28d. However, it can also be
observed from Fig. 7(b)–(d) that the self-healing degree of M1-
CM declines progressively with crack age growing. After healing
for 28d, the healing degree of specimens of crack age 7d, 28d,
and 112d descends to <66%, <43%, and <25% respectively. And even
if the healing time extends to 112d, cracks cannot be completely
repaired. It is clear that the self-healing capacity of specimens
without mineral admixtures is limited when the crack age exceeds
7d.
Fig. 8 shows the healing degree of cracks in specimens blended
with 30% FA. It can be seen that the healing degree of M2-FA30
does not decrease monotonically with crack age, which is obvi-
ously different from the result of M1-CM. At the crack age of 3d,
cracks can be completely healed within 28d since the hydration
degree of matrix is low at that age. Besides, the fact that the aver-
age initial crack width of M2-FA30-3d is smaller (0.204 mm in
Fig. 8(a)) is also accountable for it. At the crack age of 7d, the heal-
ing degree of M2-FA30 drops significantly compared with that of
M2-FA30-3d and that of M1-CM-7d. The pozzolanic effect of FA
mainly works at the late age, and consequently, the 30% replace-
ment of cement with fly ash in M2-FA30 might retard the hydra-
tion process, and thus decrease the formation of healing products
[29]. And maybe it is just because the role of FA in later hydration
that the self-healing capacity of M2-FA30 does not decrease signif-
icantly at the late crack age. From Fig. 8(c) and (d), it can be found
that at the crack age of 28d and 112d, the maximum healing degree
of M2-FA30 approximates 100% and 40% respectively after healing
for 28d, which is much better than that of M1-CM at the same age.
Moreover, the healing degree increases continuously with healing
time, suggesting that matrix mixed with FA possesses persistent
healing capacity. Furthermore, the average crack width of M2-
8
FA30-112d (0.243 mm in Fig. 8(d)) is significantly smaller than that
of M1-CM-112d (0.351 mm in Fig. 7(d)), which may also lead to the
difference of healing degree between them and will be discussed in
the following section.
The healing degree of cracks of specimens blended with 30% SL
is shown in Fig. 9. It can be observed that the healing degree of M3-
SL30 does not decrease monotonically with crack age, and differs
from the change trend of that of M2-FA30. At the crack age of 3d,
the self-healing degree of M3-SL30 is higher than that at other
crack ages, but is significantly lower than that of M1-CM-3d.
Fig. 9(a) reveals that only one point of crack was completely healed
after 28d. The 30% replacement of cement with SL in M3-SL30
weakens the hydration effect at early age, which could be one rea-
son for the above results. But more importantly, it is probably
caused by the larger initial crack width of M3-LS30-3d. The average
initial width of the crack in M3-LS30-3d is 0.378 mm (Fig. 9(a)),
which is close to the limit value of 0.4 mm that can be healed by
autogenous healing [21–23]. Moreover, it can be seen from Fig. 9
(b) that at crack age of 7d, the healing degree of M3-SL30 further
weakens and is even lower than that of M1-CM-7d. SL, a widely
used mineral admixture, can reduce the hydration heat and tem-
perature cracking of concrete at early age [29]. Therefore, the
self-healing capacity of specimens becomes lower at the crack
age of 7d. However, compared with M3-SL30-7d and M1-CM-
28d, the self-healing of M3-SL30-28d increases obviously with
the maximum healing degree being 86% after healing for 28d, as
presented in Fig. 9(c). It is probably because that SL is greatly
involved in the on-going hydration at age around 28d, which pro-
motes the generation and accumulation of healing products, and
empowers specimens to possess superior self-healing capacity at
that age, considering that the average initial crack width of M3-
SL30-7d approximates that of M3-SL30-28d, and the average initial
crack width of M1-CM-28d is significantly smaller than that of M3-
SL30-28d (M1-CM-28d: 0.286 mm, M3-SL30-7d: 0.338 mm, M3-
H. Chang, C. Li, J. Wang et al.
SL30-28d: 0.324 mm). Furthermore, the healing degree of M3-SL30
at 112d drops significantly compared with that at other ages, and it
is even lower than that of M1-CM-112d. Therefore, the blending of
SL can prolong the age within which specimens possess high self-
healing capacity, but its effect is much limited for specimens at the
crack age of 28d.
Fig. 10 presents the healing degree of cracks in specimens
blended with 10% SF. It shows that the healing degree of M4-
SF10 decreases with crack age growing. From Fig. 10(a)–(d), it
can be found that after healing for 28d, the upmost healing degree
of M4-SF10-3d, M4-SF10-7d, M4-SF10-28d, and M4-SF10-112d is
100%, 100%, 66%, and 53% respectively, all superior to that of M1-
CM at the same ages. Moreover, the healing degree increases con-
tinuously from healing time 28d to 112d, contrasting to M1-CM
whose healing stabilizes after 28d. SF, a mineral admixture with
high pozzolanic activity [29,30], participates in hydration effect
at early stage and produces healing matters, which enables M4-
SF10 to possess high self-healing capacity at the age of 3d and
7d. Meanwhile, with high fineness and tendency of aggregation,
SF will not be consumed completely at the early stage and can play
a role in the later self-healing of concrete. The first-aggregating-t
hen-dispersing feature of SF is similar to the working mechanism
of self-healing microcapsules [5,10]. Therefore, the use of SF can
promote the self-healing capacity of matrix within crack age of
0 ~ 112d and make the self-healing of specimens more lasting.
Fig. 11 shows the healing degree of cracks in specimens blended
with 10% MK. It can be observed that the self-healing degree of
0.20~0.30mm
100
Healing degree/%
80
60
M1-CM
40 M2-FA30
M3-SL30
20 M4-SF10
M5-MK10
M6-LS10
0
3d 7d
Crack age
Fig. 13. Self-healing degree of cracks with different initial crack width ranges healed for 28 days.
0d
0d
Fig. 14. The self-healing process of cracks with different initial widths along time (M4-SF10).
Construction and Building Materials 297 (2021) 123822
M5-MK10 decreases with crack age growing. At the crack age of
3d, most points of crack can be completely repaired in 28d. At
the crack age of 7d, partial points of crack can be repaired in 28d
and the rest are healed in 56d. At crack age of 28d, the upmost
healing degree reaches 74% and develops continuously from heal-
ing time 28d to 112d. It is clear that, compared with M1-CM-7d
and M1-CM-28d, the healing effect of M5-MK-7d and M5-MK-
28d improves greatly. MK is a mineral admixture of high activity
and has the pozzolanic effect at the early age [29], which can accel-
erate the generation of healing products. Hence, the mix of MK can
improve the self-healing capacity of matrix at early age. However,
the high activity of MK makes it react early and contribute little to
the later hydration. As presented in Fig. 11(d), at the crack age of
112d, the highest healing degree of specimens after 28d is only
16% and barely changes afterwards, suggesting that MK has limited
impact on the promotion of self-healing capacity of matrix at age
around 112d.
The healing degree of cracks in specimens blended with 10% LS
is presented in Fig. 12. It can be observed that the self-healing
effect of M6-LS10 drops with the increase of crack age. Compared
with M1-CM, the healing degree of M6-LS10 decreases at the crack
age of 3d, significantly increases within crack ages of 7d ~ 28d, and
stabilizes at 112d. At the crack ages of 3d and 7d, partial points of
crack in M6-LS10 are healed completely in 28d and the rest is
healed in 56d. At the crack age of 28d, some points of crack are
healed and the others is healed to a high degree in 28d. The major
composition of LS is CaO, and it produces plenty of Ca-contained
0.30~0.35mm 0.35~0.40mm
28d 112d 3d 7d 28d 112d 3d 7d 28d 112d
Crack age Crack age
3d 7d 14d 28d
(a)) Initial crack width: 0.303 mm
7d 14d 28d 56d
(b) Initial crack width: 0.418 mm
9
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

Crack age Crack age

Relative water passing rate/%

Relative water passing rate/%
1.0 1.0 3d
3d
7d 7d
0.8 28d 0.8 28d
112d 112d
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d

(a) M1-CM (b) M2-FA30

Crack age
Relative water passing rate/%

1.0 Crack age

Relative water passing rate/%

3d 1.0 3d
7d 7d
0.8 28d 0.8 28d
112d 112d
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d

(c) M3-SL30 (d) M4-SF10

Crack age Crack age

Relative water passing rate/%

Relative water passing rate/%

1.0 1.0 3d
3d
7d 7d
0.8 28d 0.8 28d
112d 112d
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 14 28 42 56 70 84 98 112 0 14 28 42 56 70 84 98 112
Healing time/d Healing time/d

(e) M5-MK10 (f) M6-LS10

Fig. 15. Relative water passing rate of specimens blended with different kinds of mineral admixtures.

healing materials in the hydration reaction at early age [29], which

Relative water passing rate/%

1.0 Healing time: can benefit the self-healing capacity of matrix within crack age of
0.9 3d
0 ~ 28d. However, at the crack age of 112d, the upmost healing
0.8 7d
14d degree after 28d is only 22%, suggesting that LS has very limited
0.7 impact on the improvement of self-healing of matrix at late age.
28d
0.6 56d Fig. 13 presents the healing degree of specimens with different
0.5 112d initial crack width after healing for 28d. It can be observed that the
0.4 self-healing capacity of M1-CM decreases greatly after the crack
0.3 age of 7d. For cracks with initial width ranging 0.20 ~ 0.30 mm,
0.2 the blending of FA improves healing effect, but for cracks with ini-
Y=0.801-0.0077X
0.1 2 tial width greater than 0.30 mm, the healing degree of FA drops
R =0.793
0.0 significantly. Moreover, the healing degree of M2-FA30 tends to
0 10 20 30 40 50 60 70 80 90 100 grow with crack age increasing even when the initial crack width
is larger than 0.3 mm, suggesting the FA mainly functions after
Healing degree of cracks the age of 28d. The effect of SL on improving the self-healing capac-
Fig. 16. Quantitative relation between healed degree of cracks and relative water
ity is comparatively limited and only works at the crack age of 28d.
passing rate of specimens. Whereas, SF, MK, and LS can significantly strengthen the self-

10
H. Chang, C. Li, J. Wang et al.
Non-test zone
Test zone
Fig. 17. Healing effect of some cracks in test zone and non-tested zone.
Fig. 18. XRD diagrams of samples taken from paste specimens mixed with different
mineral admixtures (C = Calcite, E = Ettringite, G = Gypsum, K = Kuzelite, L = Larnite,
M = Mullite, P = Portlandite).
healing capacity of matrix, but their positive effect becomes weak
after crack age of 28d and when the initial crack width is over
0.3 mm. Meanwhile, the effect of LS on improving self-healing
capacity within crack age of 28d is the most significant.
The influence of initial crack width on healing degree can be
clearly observed from the healing degree curves of the five test
points on one crack. The smaller the initial crack width is, the
higher the overall healing degree is, which is consistent with the
findings of several previous studies [14,21–24]. For instance, as
shown in Fig. 7(a)–(d), the healing degree of cracks increases with
the decrease of initial crack width, which is also true for the data in
Figs. 8–12. Moreover, as vividly presented in the digital photos of
cracks (see Fig. 14) during healing, cracks with smaller initial width
heals faster. Besides, it can also be found from Figs. 7–12 that, the
smaller the standard deviation of the five test points on one crack
is, the more concentrating the curves of healing degree are. Other-
wise, the curves are more dispersive (see Figs. 8(a), (c), (b), 9(c), 10
(c), 11(b), 12(c) etc.). Obviously, the difference of crack width is the
causation.
11
Construction and Building Materials 297 (2021) 123822
Non-test zone
Test zone
Fig. 19. XRD diagrams of healing products taken from specimens mixed with
different mineral admixtures (A = Anorthite, C = Calcite, P = Portlandite, Q = Quartz).
3.2. Water permeability
Fig. 15 presents the relative water passing rate of different spec-
imens. It can be observed that the relative water passing rate of all
specimens decreases with healing time increasing. According to
the experiment results in Section 3.1, cracks are filled gradually
with the increase of curing time, which makes water passing more
difficult and decreases water permeability. Besides, it can be found
from Fig. 15 that the relative water passing rate drops rapidly at
the early stage, then slows down, and stabilizes gradually, also
conforming to the healing process of cracks in general.
Fig. 15(a) shows the relative water passing rate of pure cement
specimens. It is clear that the relative water passing rate generally
decreases with crack age growing. After healed for 28d, the relative
water passing rate of M1-CM-3d, M1-CM-7d, M1-CM-28d, and
M1-CM-112d is 0.02, 0.35, 0.57, and 0.54 respectively. It illustrates
that the self-healing ability of specimens without mineral admix-
tures becomes insufficient after the crack age of 7d.
The relative water passing rate of specimens blended with 30%
FA is shown in Fig. 15(b). It can be observed that the relative water
H. Chang, C. Li, J. Wang et al.
Fig. 20. SEM-EDS results of healing products taken from healed cracks in M1-CM.
Fig. 21. SEM-EDS results of healing products taken from healed cracks in M2-FA30.
passing rate of M2-FA30 does not decline monotonically with crack
age growing. After healing for 28d, the relative water passing rate
of M2-FA30-3d and M2-FA30-7d is 0.11 and 0.48 separately, both
higher than that of M1-CM without FA; and the relative water
passing rate of M2-FA30-28d is 0.38, obviously lower than that
of M1-CM-28d. The evolution of relative water passing rate is con-
sistent with that of healing degree within the crack age of 28d,
which further demonstrates the feature of FA affecting the self-
healing capacity of specimens.
Fig. 15(c) presents the relative water passing rate of specimens
blended with 30% SL. The relative water passing rate of M3-SL30
does not decreases monotonically with crack age growing. Espe-
cially, the relative water passing rate of M3-SL30-7d healed for
12
Construction and Building Materials 297 (2021) 123822
Spot 1: CaCO3
Spot 1: C-S-H
Spot 1: CaCO3
28d (0.63) is the highest among all others. Moreover, it is obvious
that the relative water passing rate of M3-SL30-3d, M3-SL30-7d,
and M3-SL30-112d is all higher than that of M1-CM. However,
the relative water passing rate of M3-SL30-28d (0.50) is lower than
that of M1-CM-28d, which verifies the above finding (in Sec-
tion 3.1) that the blending of SL mainly improves the self-healing
capacity of matrix at the crack age of 28d.
The relative water passing rate of specimens blended with 10%
SF is shown in Fig. 15(d). It is clear that the relative water passing
rate of M4-SF10 generally decreases with crack age increasing, and
the relative water passing rate of M4-SF10-3d is slightly greater
than that of M1-CM-3d, but greatly smaller than that of M2-
FA30-3d and M3-SL30-3d. More importantly, the relative water
H. Chang, C. Li, J. Wang et al. Construction and Building Materials 297 (2021) 123822

Spot 1: C-S-H+C-S-A-H

Spot 1: Mg-compound Spot 2: CaCO3

Fig. 22. SEM-EDS results of healing products taken from healed cracks in M3-SL30.

Spot 1: C-S-H+CaCO3 Spot 2: CaCO3

Fig. 23. SEM-EDS results of healing products taken from healed cracks in M4-SF10.

passing rate of M4-SF10-7d, M4-SF10-28d, and M4-SF10-112d
healed for 28d is 0.34, 0.34, and 0.48 separately, all lower than that
of M1-CM, M2-FA30, and M2-SL30 at the same age. It is highly con-
sistent with the evolution of healing degree of cracks in M4-SF10,
which once again proves the superior performance of SF in improv-
ing the self-healing capacity of matrix within crack age 0 ~ 112d.
Fig. 15(e) presents the relative water passing rate of specimens
blended with 10% MK. It can be observed that the relative water
passing rate of M5-MK10-3d has a similar trend with that of M5-
MK10-7d, which is also true for that of M5-MK10-28d and M5-
MK10-112d, and the relative water passing rate of the former
two is significantly lower than that of the latter two. Moreover,
the relative water passing rate of M5-MK10 at the four crack ages
is 0.18, 0.24, 0.47, and 0.47 separately with a healing time of
28 days. Obviously, compared with that of M1-CM, only the rela-
tive water passing rate of M5-MK10-3d increases a little bit, and
all others decline significantly. Therefore, the effect of MK on
improving the self-healing capacity of matrix is remarkable.
Fig. 15(f) presents the relative water passing rate of specimens
blended with 10% LS. After healing for 28d, the relative water pass-
ing rate of M6-LS10 at cracking ages of 3d, 7d, 28d, and 112d is
0.05, 0.24, 0.23, and 0.54 respectively. It can be found that the rel-
ative water passing rate of M6-LS10-3d and M6-LS10-112d
13
approximates that of M1-CM-3d and M1-CM-112d. However, the
relative water passing rate of M6-LS10-7d and M6-LS10-28d is sig-
nificantly lower than that of M1-CM-7d and M1-CM-28d. Espe-
cially, the relative water passing rate of M6-LS10-28d is the
lowest among all specimens at the same crack age. It is clear that
LS can significantly improve the self-healing capacity of specimens
within 28d crack age.
Fig. 16 shows the quantitative relation between the healing
degree of cracks and the relative water passing rate of specimens.
It is obvious that, conforming to the above analysis, they two pre-
sent a linear correlation regardless of healing time. As a matter of
fact, water permeability is directly related to cracks. The wider and
deeper the cracks are, the easier for moisture to penetrate into and
out matrix. As healing time increases, healing products grow for
further hydration, which fill in and narrow cracks. Meanwhile,
the entrance on crack surface may be sealed due to carbonation
effect. Therefore, after the healing degree of cracks increases, it is
more difficult for moisture not only to enter into matrix, but to
penetrate further. As a result, water permeability of matrix
declines. However, there are also some abnormities in the above
results and discussion, for instances, the relative water passing rate
of M1-CM-28d (0.57) is slightly greater than that of M1-CM-112d
(0.54); the relative water passing rate of M3-SL30-7d (0.63) after
H. Chang, C. Li, J. Wang et al.
Fig. 24. SEM-EDS results of healing products taken from healed cracks in M5-MK10.
healing for 28d is the greatest among all; and the relative water
passing rate of M5-MK10-28d approximates that of M5-MK10-
112d. All those abnormities suggest that the relative water passing
rate does not conform to the healing degree of cracks of the same
specimen. This is probably because that only the healing procedure
of five points on a crack is investigated in the experiment (see
Fig. 3), and the healing degree of other places on the crack may dif-
fer (see Fig. 17) due to the different initial crack width. Conse-
quently, water will penetrate into matrix through other than the
five points, leading to the inconsistency between healing degree
and relative water passing rate since water can also penetrate into
the matrix through other parts of the crack besides the five points.
In addition, the general consistency between water permeabil-
ity and crack healing degree further reveals the features of each
kind of mineral admixtures at different ages. SL plays a limited role
in improving the self-healing capacity of matrix; FA mainly works
on the self-healing improvement of matrix after the crack age of
7d; MK and SL, especially SL, functions well in improving the
self-healing capacity of matrix within crack ages of 0 ~ 28d; SF ben-
efits the improving of the self-healing capacity of matrix through-
out the whole 112d crack age. On above, to better improve the self-
healing performance of cementitious-based materials through
replacing part of cement with mineral admixtures, a reasonable
and optimized mix should be proposed based on the feature of
every mineral admixture influencing the self-healing capacity of
matrix.
3.3. Healing products
To achieve a better understanding of the main compositions of
healing products and the difference between healing products and
the corresponding hydration products, the XRD diagrams of paste
14
Construction and Building Materials 297 (2021) 123822
Spot 1: C-S-H+
C-S-A-H
Spot 1: CaCO3
samples of different mixes and of healing products in cracks of
mortar specimens were both obtained, shown in Figs. 18 and 19
separately. As can be seen in Fig. 18, hydration products mainly
consist of calcium hydroxide (Ca(OH)2), calcium carbonate(CaCO3),
and other minerals like, mullite and kuzelite. And certainly, cal-
cium silicate hydrate gel (C-S-H), the most important one, is also
included though it cannot be directly presented in the XRD pattern.
The hydration products of paste samples are basically the same,
with the difference existing in varied minerals induced by different
mineral additives. For instance, mullite was detected in M2-FA30
while kuzelite was detected in M3-SL30. Moreover, the relative
content of each kind of hydration product differs according to
the strength of peaks in XRD diagrams, which is resulted from
the different chemical composition of mineral admixtures.
Note that it is inevitable that sand powder would be mingled in
the healing product samples when they were ground off from
cracks, considering that mortar specimens were used in this study.
Therefore, a significant quartz peak appears in every XRD pattern,
as shown in Fig. 19. Moreover, it can be observed from Fig. 19 that
there is a faint portlandite peak in the XRD patterns of M1-M5, sug-
gesting considerable loss of Ca(OH)2 in healing products. This is
partially because that some Ca(OH)2 participates in the pozzolanic
reaction of mineral admixtures in the healing process. To be speci-
fic, FA contains plenty of SiO2 and Al2O3 which react with Ca(OH)2
and produce C-S-H and calcium aluminate hydrate gel (C-A-H) as
part of healing materials [29]. Based on the SEM-EDS results of
the healing products in cracks of M2-FA30 (see Fig. 21), it can be
found that there is a mass of C-S-H gel. SL consists of lots of SiO2,
Al2O3, and CaO, and they will react with water to produce C-S-H
gel, but the reaction involved is very slow and weak. However,
once SL is mixed in cement, the Ca(OH)2 produced by cement
hydration will activate SL and accelerate the production of C-S-H
H. Chang, C. Li, J. Wang et al.
Fig. 25. SEM-EDS results of healing products taken from healed cracks in M6-LS10.
[29]. And with the increase of SL dosage, partial Si in C-S-H will be
replaced by Al and form C-S-A-H gel. Moreover, SL also incorpo-
rates considerable amount of MgO, which can produce Mg-
contained compounds, one kind of healing material. As is shown
in Fig. 22, besides C-S-H gel, Mg-contained compounds are also
detected in the cracks of M3-SL30. As for SF, it contains more than
90% SiO2, which is mostly amorphous or glassy. This kind of SiO2
possesses high pozzolanic activity, which is superior to that of FA
and SL. Hence, it participates in certain hydration reactions at the
early age [29,31]. More specifically, it mainly reacts with Ca(OH)2
to produce C-S-H, which can be found in Fig. 23. Meanwhile, MK
mainly consists of SiO2 and Al2O3 and also has high pozzolanic
activity [29]. It also mainly reacts with Ca(OH)2 to produce C-S-H
gel and Al-contained compounds. C-S-H and some Al-contained
15
Construction and Building Materials 297 (2021) 123822
Spot 1: CaCO3
Spot 1: CaCO3
Spot 1:
Mg-compound
compounds can be found in Fig. 24 based on the corresponding ele-
mental composition. And LS consists of more than 85% CaO, which
produces Ca(OH)2 after contacting water. Some Ca(OH)2 will take
part in hydration reaction, but there will be large remaining, which
can be proved by Fig. 19, the XRD diagram of M6-LS10 shows the
remaining of Ca(OH)2. The remained Ca(OH)2 will react with CO2
and produce lots of CaCO3 that can fill in cracks. Therefore, speci-
mens with SL possess excellent self-healing capacity compared
with that of pure cement mortar. Meanwhile, the LS used in this
study contains certain amount of MgO, and Mg-contained com-
pounds have also been observed, as shown in Fig. 25.
Furthermore, the remained Ca(OH)2 of other mixes absent from
hydration will also react with CO2 to produce CaCO3 in cracks,
which is accountable for the growth of calcite peak in Fig. 19. From
H. Chang, C. Li, J. Wang et al.
M1-CM
M4-SF10
Fig. 26. Crack images of different specimens obtained using industrial electron microscope.
Figs. 20–25, it can be observed that masses of CaCO3 exist in the
crack of every specimen, demonstrating that CaCO3 is one major
healing product no matter which kind of mineral admixture is
mixed. In addition, it can also be found in Fig. 19 that there a strong
peak at about 28°, which represents one kind of Al-Si-contained
compound, most likely anorthite. In summary, the type and con-
tent of healing products generated are different when different
kinds of mineral admixtures are used. The mix of SF produces more
C-S-H gel; the blending of MK, FA or SL generates some Al-
contained compounds besides plenty of C-S-H gel; and the use of
LS forms more CaCO3. The composition, content, and generation
time of those healing substances endow every mineral admixture
different ability in improving the self-healing capacity of
cementitious-based materials.
In addition, a phenomenon that the healing rate of crack surface
is greatly higher than that of crack inside has been noticed when
testing crack width with the industrial electronic microscope. It
means that even if the crack surface has been completely healed,
the inside may still remain partially void, as can be observed in
Fig. 26. Qureshi [4], Sisomphon [13], Huang [14], and Jiang [24]
also discovered that phenomenon, and stated that the rapid
growth of CaCO3 at crack surface was accountable for it. The gen-
eration of CaCO3 can close the crack surface and prevent the inva-
sion of external harmful matters, but meanwhile, it hinders the
entrance of water and CO2 that are necessary for the generation
of healing products, delaying the self-healing progress of cracks.
As a result, the recovery of mechanical performance and the dura-
bility of matrix are harmed, given that the thin surface-healing
layer is fragile and cannot provide enough cohesive force for large
loadings. To solve that problem, many studies have probed into
other self-healing methods that can overcome the problem of
surface-healing, for instances, the microcapsule technique by
White [2] and Yang [10], Dong [32] et al, hollow glass fiber method
by Li [8] and Dry [9] et al, and the bacteria mineralization method
by Jonkers [33,34], Van [6], Luo and Qian [35] et al. All those meth-
ods have achieved desirable results in laboratory, and contributed
a lot to the practical application of the self-healing cementitious-
based materials. However, most of them are either costly or diffi-
cult in operation [14], and cannot be widely used in practice for
now. Hence, more efforts are still needed to perfect the self-
healing method from perspectives of cost, efficiency and
operability.
4. Conclusions
(1) With the increase of healing time, the healing degree of
cracks grows gradually, while water permeability decreases,
presenting a linear correlation.
16
Construction and Building Materials 297 (2021) 123822
M2-FA30 M3-SL30
M5-MK10 M6-LS10
(2) As for the improving of the self-healing capacity of matrix,
SL only works at the crack age of 28d; FA mainly functions
after 28d; MK and LS are extraordinary within 28d, espe-
cially LS, its effect within 28d is the most significant; and
SF works well in the whole 112d age.
(3) The healing degree of cracks increases with the decrease of
initial crack width. The effect of mineral admixtures on
strengthening the self-healing capacity of matrix is very
restricted when the initial crack width is greater than
0.30 mm and after 28d crack age.
(4) The healing substances of different mixes are mainly com-
posed of hydration products. Except for the ubiquitous pres-
ence of mass CaCO3, it can be found that, the mixing of SF is
conducive to producing more C-S-H gel; the blending of MK,
FA or SL contributes to the generation of Al-contained com-
pounds or Mg-contained compounds besides plenty of C-S-H
gel; and the use of LS leads to the most CaCO3 production.
(5) To better improve the self-healing capacity of cementitious-
based materials through the method of replacing part of
cement with mineral admixtures, it is suggested to come
up with a rational and optimized mineral admixture compo-
sition based on the feature of every mineral admixture.
5. Data availability statement
All the data used to support the findings of this study are
included within the article.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
Authors appreciate the financial supports from the National
Natural Science Foundation of China under the contract No.
51908327 and No. 52050128, the Natural Science Foundation of
Shandong Province under the contract No. ZR2019QEE017, the
Fundamental Research Funds of Shandong University under the
contract No. 31560078614117.
References
[1] Jin Z., Chang H., Du F., et al. Influence of SAP on the chloride penetration and
corrosion behavior of steel bar in concrete, Corro. Sci. 171(2020)108714.
[2] S.R. White, N.R. Sottos, P.H. Geubelle, et al., Autonomic healing of polymer
composites, Nature 409 (6822) (2001) 794–807.
H. Chang, C. Li, J. Wang et al.
[3] M. Rooij, K. van Tittelboom, N. Belie, E. Schlangen, in: Self-Healing Phenomena
in Cement-Based Materials: State-of-the-Art Report of RILEM Technical
Committee, Springer, 2013.
[4] T. Qureshi, A. Kanellopoulos, A. Al-Tabbaa, Autogenous self-healing of cement
with expansive minerals-I: Impact in early age crack healing, Constr. Build.
Mater. 192 (2018) 768–784.
[5] J. Pang, I.P. Bond, Bleeding composites-damage detection and self-repair using
a biomimetic approach, Compos. Part A: Appl. Sci. Manuf. 36 (2) (2005) 183–
188.
[6] K. Van Tittelboom, N. De Belie, W. De Muynck, et al., Use of bacteria to repair
cracks in concrete, Cem. Concr. Res. 40 (2010) 157–166.
[7] G. Song, Y.L. Mo, Increasing concrete structural survivability using smart
materials, A proposal submitted to Grants to Enhance and Advance Research
(GEAR), University of Houston, 2003.
[8] V.C. Li, Y.M. Lim, Y.-W. Chan, Feasibility study of a passive smart self-healing
cementitious composite, Compos. Part B Eng. 29 (1998) 819–827.
[9] C. Dry, Matrix cracking repair and filling using active and passive modes for
smart timed release of chemicals from fibers into cement matrices, Smart
Mater. Struct. 3 (1994) 118–123.
[10] Z. Yang, J. Hollar, X. He, X. Shi, A self-healing cementitious composite using oil
core/silica gel shell microcapsules, Cem. Concr. Compos. 33 (2011) 506–512.
[11] J.Y. Wang, H. Soens, W. Verstraete, N. De Belie, Self-healing concrete by use of
microencapsulated bacterial spores, Cem. Concr. Res. 56 (2014) 139–152.
[12] E.F. Wagner, Autogenous healing of cracks in cement-mortar linings for
grayiron and ductile-iron water pipe, Am. Water Work Assoc. 66 (1974) 358–
360.
[13] K. Sisomphon, O. Copuroglu, E.A.B. Koenders, Self-healing of surface cracks in
mortars with expansive additive and crystalline additive, Cem. Concr. Compos.
34 (2012) 566–574.
[14] H.L. Huang, G. Ye, C.X. Qian, E. Schlangen, Self-healing in cementitious
materials: Materials, methods and service conditions, Mater. Des. 92 (2016)
499–511.
[15] T. Qureshi, A. Kanellopoulos, A. Al-Tabbaa, Autogenous self-healing of cement
with expansive minerals-II: Impact of age and the role of optimised expansive
minerals in healing performance, Constr. Build. Mater. 194 (2019) 266–275.
[16] Z.H. Zhou, Z.Q. Li, D.Y. Xu, J.H. Yu, Influence of slag and fly ash on the self-
healing ability of concrete, Adv. Mater. Res. 306–307 (2011) 1020–1023.
[17] K. Van Tittelboom, E. Gruyaert, H. Rahier, N. De Belie, Influence of mix
composition on the extent of autogenous crack healing by continued
hydration or calcium carbonate formation, Constr. Build. Mater. 37 (2012)
349–359.
[18] K. Olivier, Experimental studies of self-healing cementitious materials
incorporating mineral admixtures, in: Proc. Fourth Int. Conference Self Heal.
Mater. CD, 2013, pp. 21–24.
17
Construction and Building Materials 297 (2021) 123822
[19] Jaroenratanapirom, Dechkhachorn, R. Sahamitmongkol, Effects of different
mineral additives and cracking ages on self-healing performance of mortar, in:
Proc. 6th Annu. Concr. Conf. Petchaburi, Thailand, 2010.
[20] S. Qian, J. Zhou, M.R. de Rooij, E. Schlangen, G. Ye, K. van Breugel, Self-healing
behavior of strain hardening cementitious composites incorporating local
waste materials, Cem. Concr. Compos. 31 (2009) 613–621.
[21] J. Qiu, H.S. Tan, E.H. Yang, Coupled effects of crack width, slag content, and
conditioning alkalinity on autogenous healing of engineered cementitious
composites, Cem. Concr. Compos. 73 (2016) 203–212.
[22] S.Z. Qian, J. Zhou, E. Schlangen, Influence of curing condition and precracking
time on the self-healing behavior of Engineered Cementitious Composites,
Cem. Concr. Compos. 32 (2010) 686–693.
[23] T.H. Ahn, T. Kishi, Crack self-healing behavior of cementitious composites
incorporating various mineral admixtures, J. Adv. Concr. Technol. 8 (2010)
171–186.
[24] Z.W. Jiang, W.T. Li, Z.C. Yuan, Influence of mineral additives and environmental
conditions on the self-healing capabilities of cementitious materials, Cem.
Concr. Compos. 57 (2015) 116–127.
[25] H.L. Huang, G. Ye, D. Damidot, Effect of blast furnace slag on self-healing of
microcracks in cementitious materials, Cem. Concr. Res. 60 (2014) 68–82.
[26] C. De Nardi, A. Cecchi, L. Ferrara, A. Benedetti, D. Cristofori, Effect of age and
level of damage on the autogenous healing of lime mortars, Compos. Part B
Eng. 124 (2017) 144–157.
[27] C. Qian, H. Chen, L. Ren, M. Luo, Self-healing of early age cracks in cement
based materials by mineralization of carbonic anhydrase microorganism,
Front. Microbiol. 6 (2015) 1225.
[28] V.C. Li, E. Yang, Self healing in Concrete Materials, Self healing materials,
Springer, 2007, pp. 161–193.
[29] Z.H. Shui, X.S. Wei, D.M. Wang, Modern Concrete Science and Technology,
Science Press, Beijing, 2013, pp. 108–140.
[30] P. Feng, H.L. Chang, X. Liu, S.X. Ye, X. Shu, Q.P. Ran, The significance of
dispersion of nano-SiO2 on early age hydration of cement pastes, Mater. Des.
186 (2020) 108320.
[31] X. Liu, P. Feng, X. Shu, Q.P. Ran, Effects of highly dispersed nano-SiO2 on the
microstructure development of cement pastes, Mater. Struct. 53 (2020) 4.
[32] B. Dong, Y. Wang, G. Fang, N. Han, F. Xing, Y. Lu, Smart releasing behavior of a
chemical self-healing microcapsule in the stimulated concrete pore solution,
Cem. Concr. Compos. 56 (2015) 46–50.
[33] H. Jonkers, Self healing concrete: a biological approach, in: S. Zwaag (Ed.), Self
Healing Materials, Springer, Netherlands, 2008, pp. 195–204.
[34] H.M. Jonkers, A. Thijssen, G. Muyzer, O. Copuroglu, E. Schlangen, Application of
bacteria as self-healing agent for the development of sustainable concrete,
Ecol. Eng. 36 (2) (2010) 230–235.
[35] M. Luo, C.X. Qian, R.Y. Li, Factors affecting crack repairing capacity of
bacteriabased self-healing concrete, Constr. Build. Mater. 87 (2015) 1–7.