Accepted Manuscript

Self-healing performance of aged cementitious composites

Gürkan Yıldırım, Arash Hamidzadeh Khiavi, Seda Yeşilmen, Mustafa Şahmaran

PII: S0958-9465(17)30997-6
DOI: 10.1016/j.cemconcomp.2018.01.004
Reference: CECO 2973

To appear in: Cement and Concrete Composites

Received Date: 5 November 2017

Revised Date: 19 December 2017
Accepted Date: 2 January 2018

Please cite this article as: Gü. Yıldırım, A.H. Khiavi, S. Yeşilmen, M. Şahmaran, Self-healing
performance of aged cementitious composites, Cement and Concrete Composites (2018), doi: 10.1016/
j.cemconcomp.2018.01.004.

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 ACCEPTED MANUSCRIPT
1 Self-healing Performance of Aged Cementitious Composites
2 Gürkan Yıldırıma, Arash Hamidzadeh Khiavia, Seda Yeşilmenb, Mustafa Şahmaranc*
a
3 Department of Civil Engineering, Adana Science and Technology University, Adana, Turkey
b
4 Department of Civil Engineering, Çankaya University, Ankara, Turkey
c
5 Department of Civil Engineering, Hacettepe University, Ankara, Turkey
6

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7 Abstract
8 This study investigates the autogenous self-healing capability of one-year-old engineered

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9 cementitious composites (ECC) with different mineral admixtures to understand whether self-
10 healing performance in late ages is similar to that of early ages. Sound and severely pre-cracked

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11 specimens were subjected to different environmental conditions including water, air, “CO2-
12 water,” and “CO2-air” for one year plus 90 days of initial curing. Self-healing performance of
13 ECC mixtures was assessed in terms of crack characteristics, electrical impedance testing, rapid

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14 chloride permeability testing and microstructural analysis. Laboratory findings showed that the
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15 presence of water is crucial for enhanced autogenous self-healing effectiveness, regardless of
16 mixture composition. “CO2-water” curing resulted in the best self-healing performance of all
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17 curing conditions, which was confirmed with results from different performance tests throughout
18 the experimental study. By further curing specimens under “CO2-water” (depending on the ECC
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19 mixture composition), cracks as wide as half a millimeter (458 µm) were easily closed by
20 autogenous self-healing within only 30 days of further curing, and all cracks closed completely
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21 after 90 days. Because high levels of CO2 emission are a global problem, the effectiveness of
22 “CO2-water” curing in closing microcracks of aged cementitious composites specimens through
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23 autogenous self-healing can help reduce the increasing pace of CO2 release. The results of this
24 study clearly suggest that late-age autogenous self-healing rates of ECC specimens can be
25 significantly enhanced with proper further environmental conditioning and mixture design.
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26
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27 Keywords: Engineered Cementitious Composites (ECC); Self-healing; Curing Conditions;

28 Electrical Impedance; Rapid Chloride Permeability.
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32

*:
Corresponding author, Phone: +90-312-297-6991
e-mail: sahmaran@hacettepe.edu.tr

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33 1. Introduction

34 Engineered Cementitious Composites (ECC) are feasible new-generation concrete materials

35 for suppressing crack initiation and further growth of crack width [1-3]. ECCs are one of a
36 special branch of High Performance Fiber-Reinforced Cementitious Composites (HPFRCCs) and
37 are characterized by superior tensile ductility due to the formation of multiple microcracking.
38 The ability of ECC to exhibit multiple microcracks with typical widths of less than 100 µm is a

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39 direct consequence of pseudo strain-hardening behavior [4]. Tight microcracking is one of the
40 key parameters in increasing the time to initiation of deterioration, slowing down the rate of

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41 deterioration, prolonging the serviceability of structures and, last but not least, favoring self-
42 healing capability with no external interference (autogenous self-healing) [4-9].

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43 To date, ECCs incorporated with different polymeric fibers such as polyethylene (PE) [10],
44 polyvinyl alcohol (PVA) [11], and high tenacity polypropylene (HTPP) [12] have been
45 successfully manufactured without sacrificing multiple microcracking behavior. Moreover, the
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latest efforts have shown that polymeric fibers (e.g., PVA) in ECCs can alternatively be
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47 substituted with eco-friendly natural fibers (e.g., hemp and flax) after chemical surface treatment
48 [13,14]. Despite the effectiveness of different fibers on composite materials’ multiple
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49 microcracking behavior, due to the cost of polymeric fibers, most studies have been centered on
50 less expensive PVA fiber-based ECC mixtures.
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51 Due to concerns about uniform distribution of fibers and ultimate tensile ductility, no coarse
52 aggregates are used in ECC production, therefore overall Portland cement amount as the binding
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53 phase for the mixtures is significantly high. However, considering the high energy consumption,
54 negative environmental impact of Portland cement production, along with its dimensional
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55 stability problems, Portland cement content in ECC is generally reduced by replacing it with
56 high volumes of pozzolanic materials such as fly ash, slag, limestone powder and metakaolin.
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57 Use of pozzolans in high volumes contributes to the superior tensile ductility and durability
58 characteristics of ECC [15]. It has also been reported that the degree of autogenous self-healing
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59 is dependent on the composition of cementitious composites, and it increases along with the ratio
60 of pozzolan/cement [16,17]. This effect is due to the kinetic nature of pozzolanic reactions and
61 the higher long-term availability of unreacted pozzolanic materials compared to Portland cement.
62 However, even when high amounts of pozzolans are used in ECC production, autogenous self-
63 healing of very mature specimens may not be as effective as the younger ones due to inadequate
64 availability of portlandite and moisture in the long term.

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65 It is notable that most self-healing studies, use ECC specimens subjected to initial pre-
66 cracking at 28 days of age or earlier [5-7,15-17]. Therefore, understanding of the self-healing
67 performance of aged ECC is very limited. To account for this, recent studies focusing on the
68 self-healing performance of 180-day-old (medium-term) ECC specimens [4,18-20] were
69 performed. In a different study, HPFRCC specimens subjected to the longest initial curing period
70 (11 months) before the application of pre-cracking for self-healing assessment were utilized [21].

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71 However, considering the significantly high cracking occurrence at late ages and its
72 detrimental effects on the structural service life, more information is needed about the lifespan of

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73 self-healing in aged ECC. Therefore, contrary to the majority of self-healing studies of early-age
74 ECC specimens and those focusing on medium-term self-healing, this research investigated

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75 autogenous self-healing capability of very mature (one-year-old) ECC specimens produced with
76 different pozzolans (Class-F fly ash, Class-F fly ash with hydrated lime, ground granulated blast
77 furnace slag) and cured under different environmental conditions (water, air, CO2-water and

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78 CO2-air). In addition to commonly preferred environments for further curing (e.g. water and air),
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79 CO2-rich environmental conditioning options (e.g. CO2-water and CO2-air) were also tested; up
80 to certain limit, they may be advantageous for capturing increased CO2 concentrations in the
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81 atmosphere. These research findings are expected to provide useful data for understanding the
82 effectiveness of autogenous self-healing capability of ECC, regardless of the time of damage
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83 occurrence (i.e. cracking) and under a wide spectrum of environmental exposures.

84
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85 2. Experimental program

86 2.1. Ingredients, proportioning, manufacturing and initial curing of mixtures

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87 ECC mixtures produced in this study were composed of CEM I 42.5R type ordinary
88 Portland cement (PC), fine silica sand with a maximum aggregate size of 0.4 mm, specific
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89 gravity of 2.60 and water absorption capacity of 0.3%, potable mixing water, liquid
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90 polycarboxylic ether-based high-range water reducing admixture (HRWRA) with solid content
91 of 40% and polymeric PVA fibers at 2% of mixture volume, with a diameter of 39 µm, length of
92 8 mm, nominal tensile strength of 1610 MPa, elastic modulus of 42.8 GPa, maximum elongation
93 of 6%, and specific gravity of 1.3. Mixtures also incorporated pozzolanic materials including
94 Class F fly ash (FA, ECC-FA) and ground granulated blast furnace slag (GGBFS, ECC-S). An
95 additional mixture (ECC-FA/CH) was manufactured by incorporating 5% commercially
96 available hydrated lime (CH) by total weight of cementitious materials (i.e. PC + FA) into the

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97 ECC-FA mixture. Chemical and physical properties of PC, FA, GGBFS and silica sand are
98 illustrated in Table 1.
99 All mixtures were produced with a constant water to cementitious materials ratio (W/CM)
100 of 0.27 and pozzolanic materials to PC ratio of 1.2, by weight. Mixture proportions are presented
101 in Table 2. During mixing, all dry components of the matrix (PC, FA, GGBFS, CH and sand
102 [changed depending on the mixture type]) were mixed together, then pre-weighed water and high

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103 range water reducing admixture were added. Finally, fibers were slowly added and dispersed.
104 HRWRA amount was not kept constant in different mixtures due to varying fineness values of

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105 specific ingredients, and was therefore adjusted in accordance with the desirable fresh mortar
106 properties to favor fiber distribution.

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107 All tests performed in this study used Ø100×50 mm cylindrical specimens. For extraction of
108 smaller scale cylinders to be used in tests, Ø100×200 mm cylindrical specimens were cast using
109 different ECC mixtures. After initial casting of fresh mixtures, Ø100×200 mm cylindrical

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110 specimens were kept in their molds for 24 hours at 50±5% RH and 23±2 oC, with their surfaces
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111 covered with plastic sheets. After 24 hours, specimens were taken out of their molds. Initial
112 curing in isolated plastic bags at 95±5% RH and 23±2 oC was initiated on the second day to the
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113 end of one year. After a year of initial curing, Ø100×50 mm specimens were extracted from
114 whole Ø100×200 mm specimens with a diamond blade saw.
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115
116 2.2. Initial damage introduction
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117 To monitor self-healing behavior, the one-year-old Ø100×50 mm cylinders were pre-loaded
118 under splitting tensile loading to generate cracks of varying numbers and widths. Given the
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119 different compositions of ECC mixtures, achieving similar microcracking damage with a
120 constant pre-loading level was not possible. Therefore, to determine their ultimate splitting
121 tensile deformation capacities, four Ø100×50 mm cylinder specimens from each mixture were
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122 loaded until failure at a loading rate of 0.005 mm/s using a closed-loop controlled material
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123 testing system. After testing, splitting tensile stress vs. deformation plots for each specimen were
124 drawn and deformation levels corresponding to maximum splitting tensile stress levels were
125 defined as the ultimate splitting tensile deformation capacity, with results averaged for each
126 mixture. One-year ultimate splitting tensile deformation capacities of different mixtures were
127 very similar, with levels of around 2 mm. All specimens from different mixtures with a common
128 initial pre-loading level were therefore pre-cracked to impart microcracks. A common initial pre-
129 loading level was set at 70% of ultimate splitting tensile deformation capacity of different
130 specimens, meaning that application of initial pre-loading almost caused severe failure for all

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131 specimens. In addition to the pre-loaded specimens, the same number of sound specimens was
132 also used in tests for comparison purposes.
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134 2.3. Further environmental conditioning

135 After initial pre-loading on the 365th day, reference measurements from sound and pre-
136 loaded specimens were recorded using different test methods. Beyond 365 days, further

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137 environmental curing was applied to specimens in two separate curing cabinets. Both cabinets
138 had a 120-liter capacity, and the ability to achieve relative humidity between 20-95% and

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139 temperatures between -10 – 60 °C. The only difference between the two cabinets was that
140 Cabinet II was able to achieve a CO2 concentration of up to 20% in the controlled environment.
As seen in Fig. 1, Cabinet I was set to achieve a controlled environment with 50±5 oC and

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142 50±5% RH, while Cabinet II was set to 50±5 oC, 50±5% RH and 3% CO2 concentration. Each
143 cabinet also contained a separate container for submerging specimens in water. Specimens (both

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144 sound and pre-loaded) cured in air in Cabinet I at 50±5 oC, 50±5% RH are shown as “air,” while
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145 specimens cured in water in Cabinet I at 50±5 oC, 50±5% RH are shown as “water.” The same
146 procedure was followed for Cabinet II (Fig. 1).
147 To account for possible variations in each of the proposed environmental conditioning, four
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148 sound and pre-loaded specimens from each mixture were used for each rapid chloride
149 permeability [RCP] and electrical impedance [EI] test. The further environmental conditioning
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150 lasted for 90 days, with RCP and EI tests repeated after each 15-day interval. A temperature
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151 range of 50±5 oC was selected based on the conclusions of Reinhardt and Jooss [22], who stated
152 that high temperatures are favorable for faster self-healing kinetics. An RH level of 50±5% was
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153 selected and a separate water container was used in each cabinet, since self-healing is reported to
154 be more pronounced in fully and/or partially wet conditions [23]. The RH level was also selected
155 because it favors calcium carbonate precipitation through carbonation reactions, which is
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156 reported to be one of the main mechanisms significantly contributing to autogenous self-healing
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157 [24]. There is a consensus between the results of carbonation tests conducted at natural and/or
158 below 4% CO2 concentrations, indicating that this type of accelerated test can be used to interpret
159 probable long-term carbonation effect [25], which can influence long-term self-healing of
160 microcracks. Hence, in Cabinet II, CO2 level was set at 3%. By comparing self-healing
161 performances of specimens placed in different cabinets, the influence of promoted carbonation
162 reactions on autogenous self-healing of ECCs was more clearly assessed.
163
164 2.4. Proposed testing methods for self-healing

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165 Electrical impedance (EI) measurements were recorded from different Ø100×50 mm
166 cylindrical specimens to assess self-healing, using a concrete electrical resistivity meter with
167 uniaxial configuration. Details of the electrical resistivity meter and proposed EI testing to assess
168 autogenous self-healing of cementitious composites have been thoroughly discussed in the recent
169 works of the authors [26,27], thus no further explanations were provided here.
170 One of the most important considerations for EI testing is the individual moisture states of

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171 specimens during testing. Since electrical measurements can be affected by extra moisture and
172 high temperature levels after curing under different conditions, various drying/cooling

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173 procedures were followed for specimens cured in air and water in each cabinet before EI testing.
174 After being removed from the cabinets on specified days, air-cured specimens were left out in a
controlled room at 50±5% RH, 23±2 oC for 24 hours. When water-cured specimens reached

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176 testing age, they were dried out in an oven at 60 oC for around 24 hours, then allowed to cool in a
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177 controlled room at 50±5% RH, 23±2 C for another 24 hours. Drying duration and

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178 environmental conditions were determined based on specimens reaching a constant weight at
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179 room temperature. The difference between any two successive weight measurements was less
180 than 0.5% of the lowest value obtained. All specimens were tested at similar moisture states.
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181 Rapid chloride permeability (RCP) testing, conducted according to the ASTM C1202 [28]
182 standard, was also used to evaluate self-healing of ECC specimens. RCP tests were performed on
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183 water-saturated specimens and results were recorded in terms of electrical charge passed in
184 Coulomb (C).
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185 In addition to EI and RCP tests, visual observations of microcracks were also made before
186 and after self-healing occurrence using a video microscope with 125× magnification capability.
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187 For each given mixture and curing condition, specified ages and results recorded from specimens
188 used for RCP and EI tests were averaged and microcrack characteristics were measured from a
189 specific surface based on those averages.
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190 Finally, after 90 days of further curing in different environmental conditions, ultimate self-
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191 healing products from different ECC mixtures were further analyzed using thermogravimetry
192 (TGA/DTG), X-ray diffraction (XRD) and scanning electron microscopy (SEM). For
193 thermogravimetric analysis, powder samples weighing approximately 50 mg were subjected to
194 temperatures escalating from room temperature to 1050°C at a rate of 10°C/min. Temperature
195 exposure occurred in a carbon dioxide-free environment with 100 ml/min nitrogen flow. Before
196 grinding, specimens were kept in acetone up to testing to stop the hydration process. For the
197 chemical evaluation of final self-healing products, XRD analyses were performed on powder
198 samples gently scratched with a razor from the surfaces of healed microcracks of ECCs

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199 subjected to different further environmental conditions. These samples had an approximate
200 weight of 20 mg and particle size of less than 150 µm. Chemical compositions of self-healed
201 microcracks were further detailed with SEM micrographs.
202
203 3. Experimental results

204 3.1. Crack characteristics

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205 Before being exposed to further environmental conditioning, crack widths of ECC
206 specimens were measured after initial pre-loading. In Fig. 2, densities of crack width

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207 measurements are presented. While constructing this figure, 3-parameter Weibull distribution
208 which had the best fit was selected among various distributions. Fig. 2 shows a higher number of

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209 microcracks with smaller widths in ECC-FA specimens. For example, after initial pre-loading,
210 ECC-S specimens exhibited a smaller number of microcracks with widths of less than 100 µm
211 and a larger number of microcracks with widths higher than 150 µm. Microcracks formed over
212
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ECC specimens with slag after initial pre-loading had a tendency to have larger openings than
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213 those containing fly ash. Replacing Portland cement with slag led to a stronger matrix in
214 comparison to fly ash, resulting in cracks with larger widths and spacing.
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215 Previous comparisons between ECC systems in which Portland cement was replaced with
216 slag and fly ash showed similar behavior [23,26,29]. ECC-FA/CH specimens also exhibited
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217 wider cracks than ECC-FA. This behavior can be explained using the same argument made for
218 ECC-S specimens: adding hydrated lime (CH) to ECC-FA systems favors pozzolanic reactions
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219 in the long term, resulting in a stronger matrix and a higher probability for fiber rupture rather
220 than fiber pull out upon loading, and therefore a smaller number of cracks with larger widths
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221 [30]. Clear [31] reported that in order for a crack to be healed completely, crack width should be
222 less than 300 µm. Based on this finding and the data in Fig. 2, it is possible that almost all
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223 purposely-introduced microcracks with different widths upon initial pre-loading can be healed
224 autogenously, regardless of mixture type.
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225 Despite the suggestion made by Clear [31], studies conducted by Jacobsen et al. [16],
226 Şahmaran and Yaman [32], Reinhardt and Jooss [22], Edvardsen [33] and Aldea et al. [34]
227 proposed that for pronounced self-healing, crack widths should not be more than 5-10 µm, 50
228 µm, 100 µm, 200 µm and 205 µm, respectively. Based on these suggestions, the long-term self-
229 healing performances of ECC mixtures further cured under different conditions were analyzed
230 with respect to initial crack width. Fig. 3 shows 90-day self-healing performances of ECC
231 mixtures under different curing conditions for specimens with microcrack widths of less than

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232 100 µm, between 100 and 200 µm, and more than 200 µm. Percental improvements given in Fig.
233 3 were formulated as [1 ˗ (crack width after 365+90 days/crack width after 365 days) × 100].
234 Calculations of improvements were made for each microcrack and average of results for a
235 specific range of crack width was shown in Fig. 3.
236 Fig. 3 shows that all specimens demonstrated a certain extent of self-healing in all curing
237 conditions. Irrespective of initial crack widths, self-healing rates of specimens cured under water

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238 were always higher than those cured in air. Depending on the mechanism (i.e. further hydration
239 and calcium carbonate precipitation), necessary elements such as moisture and CO2 needed to

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240 find their own way through the microcracks to heal them. Although the selected humidity level
241 of 50±5% RH is high enough for considerable self-healing to take place, there is a clear

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242 difference between being submerged in water and letting specimen surfaces be exposed to
243 external moisture without high osmotic pressure. The pronounced self-healing capability of
244 submerged specimens can therefore be related to the continuous availability of moisture near

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245 crack surfaces. When water curing applied in Cabinets I and II is compared, the effect of high
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246 CO2 exposure on the self-healing capability of ECC specimens can be more easily visualized.
247 Fig. 3 shows that self-healing rates of specimens submerged in water in Cabinet II (with CO2
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248 level of 3% [CO2-water curing]) were higher for all initial crack widths and all mixtures. The
249 effectiveness of water curing under a CO2-rich environment compared to water curing in
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250 atmospheric CO2 conditions became much more pronounced for microcracks with initial widths
251 larger than 200 µm. It is widely accepted that carbonation reactions are terminated when
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252 concrete material is too dry (RH<40%), since CO2 cannot dissolve to produce carbonic acid
253 (H2CO3) with insufficient water. When concrete is saturated (RH>90%), carbonic acid is unable
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254 to penetrate into the saturated pores and diffuse throughout the concrete, again preventing
255 carbonation.
256 In Cabinet II, environmental conditioning was set at 50±5 oC, 50±5% RH, 3% CO2. In this
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257 environment, the goal was to dissolve the high concentration of CO2 at an ideal range of relative
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258 humidity (50±5% RH), to obtain carbonic acid and then saturate the curing water with it. When
259 carbonic acid diffuses into concrete material, it can react with calcium hydroxide (CH) to
260 produce calcium carbonate through direct carbonation. Moreover, after being diffused into
261 concrete, it can be reduced into bicarbonate (HCO3–) and carbonate (CO32–) ions, depending on
262 the pH value of pore solution. These carbonates may react with Ca2+ ions leached away from
263 both CH and calcium silicate hydrate (C-S-H) gels to form calcium carbonate [23,26]. The more
264 pronounced self-healing performance in CO2-water curing was therefore largely attributed to

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265 direct carbonation reactions and calcium carbonate precipitation, and slightly to further hydration
266 reactions in a completely wet environment. These results are further detailed later in this paper.
267 To achieve complete healing of microcracks, width is important; considering the total
268 amount of product that needs to be produced via different self-healing mechanisms. The
269 importance of initial microcrack widths can be visualized more easily by looking at Fig. 3. When
270 the self-healing performances of microcracks of different widths are compared for different ECC

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271 specimens further exposed to CO2-water curing, at least 77% of all microcracks with widths of
272 less than 100 µm were completely healed. When initial crack widths of specimens under the

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273 same curing condition were greater than 200 µm, more than half (52%) were completely healed.
274 Table 3 displays crack characteristics of different ECC mixtures. It also shows that

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275 depending on mixture type, cracks of up to 458 µm in one-year-old specimens can be healed
276 completely after 90 days of CO2-water curing. Moreover, 90 days was more than enough for
277 complete closure of large cracks, even after 15 days of further curing significant amounts of self-

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278 healing products were observed on the surface of cracks (Fig 4). Most self-healing studies have
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279 concluded that self-healing rate is much more pronounced in early-age specimens, given the
280 abundance of unhydrated cementitious components to be further hydrated and fill microcracks.
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281 Nevertheless, the current study suggests that along with the high early-age self-healing rate of
282 ECC specimens reported in literature, late-age self-healing rates of aged ECC specimens can be
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283 similar to early-age with proper further environmental conditioning and mixture design. These
284 results could answer the long-standing question of whether autogenous self-healing in the
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285 microcracks of aged ECCs is as effective as it is in younger specimens.

286 Based on their compositions, different ECC mixtures resulted in different self-healing
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287 performances. Fig. 3 shows that for almost all curing conditions and initial crack widths, self-
288 healing performance of ECC-FA was more pronounced. Superior self-healing performance of
289 ECC-FA was much more evident under CO2-water curing for all crack widths; the 90-day
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290 healing rate of ECC-FA specimens with widths of less than 100 µm was 100% under CO2-water
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291 curing beyond 365 days of initial curing. For ECC-FA specimens with initial crack widths
292 between 100 µm and 200 µm and larger than 200 µm under the same curing conditions, healing
293 rates were 99.4% and 98.8%, respectively. It is interesting to note that under CO2-water curing,
294 cracks up to 458 µm wide were healed even after an additional 30 days (Table 3 and Fig. 4).
295 Under certain environmental conditioning, completely self-healed maximum microcrack widths
296 (458 µm) recorded from aged ECC-FA specimens were considerably higher than those reported
297 in literature [16,22,31-34]. ECC-FA specimens exhibited higher self-healing rates under CO2-

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298 water curing due to the precipitation of calcium carbonate, as will be further detailed in
299 forthcoming sections.
300 In terms of crack plugging, performance rankings of other mixtures changed depending on
301 crack width and further curing conditions. In general, ECC-FA was followed by ECC-FA/CH
302 and ECC-S. However, despite their lower crack healing performances compared to ECC-FA
303 (Fig. 3), maximum crack widths of completely self-healed microcracks in ECC-FA/CH (356 µm)

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304 and ECC-S (397 µm) mixtures were still well above the threshold of 300 µm mentioned by Clear
305 [31].

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306
307 3.2. Electrical impedance (EI)

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308 3.2.1. One-year-old specimens

309 Direct electrical measurements (electrical impedance – EI) recorded from sound and pre-
310 loaded ECC specimens for different further curing conditions are shown in Fig. 5. At the time of
311
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each EI testing, special care was taken to bring all ECC specimens subjected to different
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312 environmental conditions to a similar moisture state (by reaching constant weight conditions) in
313 order not to risk the sensitivity of EI measurements.
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314 There were minor differences in the EI values of one-year-old sound ECC specimens.
315 Electrical resistivity testing is a commonly used method to evaluate microstructural properties of
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316 cement-based composites, which is largely influenced by the changes in porosity, pore solution
317 chemistry, pore network tortuosity and moisture state at the time of testing [35]. After 365 days,
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318 sound specimens of different mixtures resulted in similar microstructural properties with similar
319 maturity, making EI results very close. On the other hand, upon initial pre-loading for crack
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320 introduction, average EI results of one-year-old sound ECC specimens increased dramatically
321 (Fig. 5), although increment rates were very different depending on mixture type. For example,
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322 average one-year EI results of ECC-FA specimens to be subjected to 90 days of further curing
323 were 58 kΩ, while the same value increased by 117% – reaching 126 kΩ – for pre-loaded
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324 specimens of the same age. For ECC-FA/CH and ECC-S specimens, similar increment rates with
325 initial pre-loading were 170% (46 kΩ to 124 kΩ) and 479% (38 kΩ to 220 kΩ), respectively.
326 More pronounced increments noted in the EI results of sound ECC-S specimens upon initial pre-
327 loading were attributed to decisiveness of crack width values on individual EI results rather than
328 crack numbers (see Section 3.1) [26,27]. Another reason for the higher increments in EI results
329 of ECC-S upon initial pre-loading may be the influence of PVA fibers bridging opposite crack
330 faces. Although PVA fibers are non-conductive, they are covered with fragments of conductive

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331 cementitious matrix. Given the higher fracture toughness and fiber-to-matrix chemical bonding
332 of ECC-S specimens, more fibers are likely to break than be pulled out under loading, which
333 reduces the chance for crack bridging and contributes to higher increment rates in EI results of
334 pre-loaded ECC-S.
335
336 3.2.2. Effects of further environmental conditioning beyond initial 365 days of curing

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337 The changes in average EI results of sound and pre-loaded specimens with 90 days of
338 different environmental conditioning are shown in Fig. 5. This figure showed that although

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339 water-cured specimens were dried to reach a similar moisture state throughout EI testing, the
340 inner pores of ECC specimens remained saturated. As a result, EI results of water- and air-cured

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341 specimens showed a large difference for both sound and pre-loaded specimens. Therefore, it was
342 decided to compare the results of water- and air-cured specimens among themselves.
343 Almost all EI results of sound specimens of ECC mixtures subjected to air curing

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344 (regardless of CO2 exposure) increased continuously until the end of 365+90 days. Although
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345 ECC specimens were older than one year at the time of testing, continuous increments in the EI
346 results of sound ECC specimens were attributed to the densification of cementitious paste, which
347 further reduced both the amount of pore solution transporting conductive ions and the number of
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348 least-resistive paths. For further air-cured sound ECC specimens, EI values and rates of
349 increment in EI values of ECC-FA mixtures were the highest among different ECCs, especially
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350 when compared to ECC-S mixture. For example, while EI results of sound specimens further
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351 cured for 90 days under CO2-air conditioning increased by 1210% (60 kΩ to 792 kΩ), the same
352 increment rates were 1103% (46 kΩ to 559 kΩ) for ECC-FA/CH and 810% (45 kΩ to 409 kΩ)
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353 for ECC-S mixtures. Similar behavior was also monitored in air conditioning without high CO2
354 concentration, albeit to a lesser extent. This behavior of further air-cured sound specimens was
355 associated with the ionic states of specimens at the time of testing. The pore solution chemistry
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356 of cementitious composites plays a key role in EI results, especially at late ages. When mixed
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357 with water, cementitious components add considerable concentrations of Na+, K+, OH-, Ca2+ and
358 SO42- ions into the mixing water. As a result of setting and early hydration, however, Ca2+ and
359 SO42- ions diminish appreciably, leaving a pore solution that is composed mainly of dissolved
360 alkali hydroxides. In an aqueous medium at 25 oC, ionic conductivities of Na+, K+ and OH- are
361 50.1, 73.5 and 198 cm2 equiv-1 Ω-1, respectively [36]. Given the significantly higher electrical
362 conductivity of OH- ions compared to other alkalis in pore fluid, and the faster consumption of
363 calcium hydroxide through pozzolanic reactions in the presence of Class-F fly ash particles, the
364 substantially higher EI results recorded at later ages are more understandable. On the other hand,

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365 the addition of external CH in ECC-FA/CH and the more pronounced cementing capability of
366 slag particles compared to pozzolanic behavior in ECC-S are likely to increase the amount of CH
367 and associated OH- ion concentrations, leading to lower increments in EI results with time.
368 Another important point to note was that average EI results of sound specimens subjected to
369 air curing with high CO2 were higher than those that were not, especially at late ages. This
370 behavior, observed with high CO2 concentration, was attributed to accelerated carbonation and

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371 its effects on pore solution chemistry. Because carbonation is known to reduce pore solution
372 alkalinity, the higher-than-expected rates of carbonation with CO2-rich air curing which
ultimately reduced the associated OH- ions in the pore solution, could be the reason for the

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373
374 abovementioned behavior of sound specimens. Carbonation is also known to reduce porosity,

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375 since the volume of carbonation products is larger than the consumed CH. Reduced porosity in
376 carbonated regions may have also played a role in further increasing the EI values of sound
377 specimens cured in CO2-rich air.

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378 Fig. 5 also shows consistent differences in the EI results of pre-loaded ECC specimens cured
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379 in air with and without high CO2 concentration. Furthermore, differences in air-cured EI results
380 of pre-loaded ECC-FA specimens with and without high CO2 concentration were much smaller
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381 than in ECC-FA/CH – and especially in ECC-S specimens – due to crack characteristics. ECC-
382 FA exhibited the smallest crack widths of all mixtures due to carbonation.
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383 Carbonation is a process that starts from the surface of the specimens, and is then governed
384 by CO2 diffusion through the surface. The largest crack widths observed in ECC-S specimens
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385 had a higher surface area and increased diffusion depths, and carbonation reactions were
386 therefore expected to be more prevalent in these specimens. Thus, the differences between EI
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387 values for pre-loaded specimens cured in air with and without high CO2 concentration were
388 larger when crack widths were larger. Fig. 5 shows that EI results of ECC-S specimens air-cured
389 under high CO2 concentration were higher than other mixtures, while EI results of ECC-S
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390 specimens air-cured under atmospheric CO2 were lower.

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391 Average EI results of sound specimens further cured under water were different than those
392 of air-cured specimens, as they did not show marked changes regardless of high CO2 exposure
393 and mixture type. Although continuous increments in EI results of water-cured sound specimens
394 were anticipated with improved matrix properties over time, and specimens were dried at 60 oC
395 for 24 hours to reach a constant weight before EI testing, no distinctive changes in values were
396 noted with further curing due to the water remaining in the isolated pores of ECC specimens.
397 Fig. 6 shows the ratio of EI values of pre-loaded specimens to sound specimens (EIPL/EIS)
398 along with the rate of crack healing against additional curing days for different ECC mixtures

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399 under different environmental conditions. The figure shows a correlation between the crack
400 healing rates and EIPL/EIS ratios of ECC specimens, suggesting that pre-loaded specimens can
401 reach original EI results of sound specimens by plugging cracks through self-healing. EIPL/EIS
402 ratios of specimens cured under water with and without high CO2 exposure converge close to
403 one, and crack healing rates of these specimens are significantly higher than those cured in air,
404 suggesting superior self-healing performance. As previously detailed and shown in Fig. 4, the

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405 most prominent self-healing of microcracks for all ECC mixtures was achieved with CO2-water
406 curing. Correlatively, the smallest EIPL/EIS ratios were recorded from CO2-water cured

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407 specimens for almost all ECC mixtures.
408 For almost all ECC specimens cured in water with and without high concentrations of CO2,

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409 most self-healing was achieved within the first additional 15 days (as also reported in Section
410 3.1), so that EIPL/EIS ratios started to stabilize around one during this period. In some instances,
411 however, convergence of EIPL/EIS ratios around one continued beyond the first 15 days. In

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412 addition to under water curing, air curing was also effective in converging EIPL/EIS ratios around
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413 one, depending on mixture type, curing condition and additional curing period. For example,
414 ECC-FA exhibited EIPL/EIS ratio of 1.235 after 90 days of additional CO2-air curing beyond the
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415 first 365 days. This suggests a certain amount of self-healing occurrence in terms of electrical
416 measurements, even when cured in air.
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417 When the self-healing performances of different mixtures are compared in terms of EI
418 results, EIPL/EIS ratios closest to one were obtained mostly from ECC-FA specimens regardless
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419 of further curing condition. This behavior was attributed not only to smaller crack widths due to
420 initial pre-loading, but also to the ionic states of specimens at time of testing (Fig. 6).
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421
422 3.3. Rapid chloride permeability (RCP)

423 3.3.1. One-year-old specimens

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424 Fig. 7 shows average RCP test results of sound and pre-loaded ECC specimens subjected to
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425 different environmental conditions. Fig. 7 clearly shows that RCP test results of all ECC
426 specimens after the initial 365 days of curing were very low. One-year RCP test results of sound
427 specimens allocated to be further cured under different environmental conditions were 150 C, 98
428 C and 186 C for ECC-FA, ECC-FA/CH and ECC-S mixtures, respectively. Although variations
429 in RCP results were small, the lowest values were recorded from sound ECC-FA/CH specimens
430 at the end of one year of initial curing.

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431 When the amount of fly ash (specifically Class-F fly ash) used in mixtures exceeds 30-40%,
432 hydration is delayed because the amount of CH formed as a result of cement hydration is not
433 sufficient to completely diminish the excessive amounts of fly ash [29]. It therefore appears that
434 adding hydrated lime to ECC specimens with high volumes of fly ash (ECC-FA) triggered the
435 pozzolanic capacity of the cementitious systems. This led to higher improvements in chloride ion
436 penetrability of ECC-FA/CH specimens by forming additional C-S-H gels and filling the empty

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437 spaces between the fine grains. Given that RCP test is an electrochemical test method, pore
438 solution chemistry is decisive on the overall results. However, compared to EI testing, RCP test

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439 is less dependent on the ionic composition of pore solution and more on its porosity and pore
440 tortuosity [27]. It can therefore be concluded that ECC-FA/CH has better permeability properties

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441 than ECC-FA due to pore refinement in the presence of extra calcium hydroxide addition.
442 Initial pre-loading of one-year-old sound ECC specimens caused RCP test results to
443 increase, since new microcracks provided new pathways for chloride ions. Average RCP test

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444 results of sound specimens allocated for further curing under different environmental conditions
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445 increased from 127 C to 514 C for ECC-FA, from 86 C to 655 C for ECC-FA/CH, and from 177
446 C to 594 C for ECC-S. Although certain increments in RCP test results were noted with initial
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447 pre-loading, and increment rates varied for different ECC mixtures, chloride ion penetrability
448 values were still in the very low range (less than 1000 C) according to ASTM C1202 standard. It
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449 is important to keep in mind that initial pre-loading was at 70% of ultimate splitting tensile
450 deformation capacity, which is a very high level of damage.
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451
452 3.3.2. Effects of further environmental conditioning beyond initial 365 days of curing
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453 Fig. 7 shows that RCP test results continuously decreased regardless of further curing
454 condition, for all sound ECC specimens from different mixtures, due to the development of
455 matrix properties with time. Depending on the further curing condition, values as low as 16 C
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456 (from ECC-FA/CH specimens further cured under CO2-water curing) were obtained from sound
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457 specimens after 365+90 days. However, no detailed discussions were made regarding the
458 changes in RCP test results of further cured sound specimens, since the values were already
459 relatively low, even at the end of 365 days of initial curing.
460 Similar to the behavior of sound specimens, average RCP test results of pre-loaded
461 specimens decreased continuously with time regardless of the type of further conditioning (Fig.
462 7). Although results decreased continuously until the end of 90 days beyond the initial 365, the
463 rate of decrements in RCP test results of pre-loaded specimens were significantly higher than
464 sound specimens for the first 15 days. This suggests pronounced self-healing achievement during

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465 this period (Fig. 7). For example, average RCP test results of pre-loaded specimens of ECC-FA,
466 ECC-FA/CH and ECC-S subjected to 15 days of further CO2-water curing improved by 79%
467 (from 527 C to 111 C), 76% (from 631 C to 152 C) and 63% (from 530 C to 196 C) respectively.
468 Results of RCP tests were in line with EI tests and analysis of crack characteristics.
469 CO2-water curing was the most effective further curing condition for lowering average RCP
470 test results of pre-loaded ECC specimens, regardless of mixture type. Water curing without high

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471 CO2 concentration was the second most effective curing condition, followed by CO2-air and air
472 curing. The effectiveness of water curing on self-healing (regardless of the CO2 concentration) in

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473 terms of chloride ion penetrability in the first 15 days of further curing is clearly illustrated in
474 Fig. 7, with steeper slopes of RCP curves for water-cured specimens than those cured in air. For

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475 effective self-healing performance, therefore, the presence of water is critically important.
476 As mentioned, RCP test is less dependent on moisture state than EI test, since RCP tests are
477 conducted under fully-saturated conditions. Results of specimens exposed to different curing

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478 conditions can more easily be compared among themselves. Looking at the first 15 days of
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479 curing, where self-healing was much more prevalent, the highest drops in permeability were in
480 ECC-FA/CH, which exhibited larger cracks compared to ECC-FA. This explains the higher
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481 permeability results recorded just after initial pre-loading. The smallest crack widths in ECC-FA
482 led to slower healing rates in terms of RCP test results, since self-healing is more diffusion-
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483 dependent when crack widths are small. In addition, self-healing rate was even slower for air-
484 cured specimens because it relies mostly on CO2 diffusion and subsequent carbonation. The
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485 permeability drop was relatively fast and high for ECC-S specimens subjected to water and CO2-
486 air curing, as the water and CO2 penetrated through the relatively large cracks formed during
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487 pre-loading. However, for specimens air cured in atmospheric CO2 levels, low levels of
488 carbonation and continuing pozzolanic reactions were less effective against such large cracks.
489 Self-healing performances of different ECC mixtures in terms of lowering RCP test results
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490 were very close to each other, although decrement rates were slightly more pronounced for ECC-
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491 FA and ECC-FA/CH, especially with water-based further curing. According to Andrade [37],
492 OH- ions in pore fluid act as supporting electrolytes and are responsible for the movement of
493 substantial amounts of charge during RCP testing, given their higher conductivity (198 cm2
494 equiv-1 Ω-1) compared to other ions present in the pore fluid (Na+, K+, Ca2+, and Cl–). The higher
495 decrement rates in RCP test results of ECC-FA specimens could therefore be related to OH- ion
496 depletion caused by diminished portlandite with further pozzolanic capability. The superior
497 performance of ECC-FA/CH in reducing RCP test results, on the other hand, was attributed to

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498 pore refinement in the presence of added calcium hydroxide. These results indicate that RCP test
499 results are more influenced by matrix properties than the ionic state of pore solution.
500
501 3.4. Self-healing products

502 Although reaction products of autogenous self-healing appear in literature, results are
503 inconsistent due to heterogeneous dispersion and time-dependent compositions of reaction

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504 products [38]. Therefore, to detail ultimate reaction products from different ECC mixtures,
505 specimens were investigated using thermo-gravimetry (TGA/DTG), X-ray diffraction (XRD)

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506 and scanning electron microscopy (SEM).
507 As mentioned earlier, the main self-healing product of ECC mixtures was calcium carbonate

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508 (CaCO3). TGA/DTG analysis was therefore used to further evaluate the precipitated CaCO3 on
509 microcrack surfaces. The presence of vaterite, aragonite, calcite and amorphous CaCO3 has been
510 reported for cementitious composites with different levels of carbonation [39]. CaCO3

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511 decomposition occurs mainly in the 500-900 °C [40] range. Amorphous forms of CaCO3 start to
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512 decompose in the same temperature range as CH [41], which complicates quantification of CH
513 or amorphous CaCO3 using TGA/DTG analysis. Thus, quantification of self-healing products
514 was limited to the polymorphs of CaCO3 in this study. The onset temperatures in TGA/DTG
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515 analysis were visually determined, and DTG peaks in the ranges of 500-600 °C, 600-750 °C,
516 750-800 °C were quantified as vaterite, aragonite and calcite, respectively, which was similar to
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517 previous studies [41,42]. Fig. 8 shows total percentages of CaCO3 calculated via TGA/DTG
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518 analysis for each ECC in accordance with the selected further curing condition.
519 Fig. 8 shows a distinct difference between vaterite amounts in specimens subjected to air
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520 and water curing for all ECC mixtures, regardless of CO2 exposure. The percentage of vaterite
521 was consistently lower in specimens subjected to water-based curing, probably due to the
522 dilution of ions in saturated medium and increased pozzolanic reactions in the presence of water.
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523 Both mechanisms decrease the pH value of pore solution, and low pH value favors the formation
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524 of aragonite over vaterite [39,43]. Additionally, the C/S ratio of C-S-H gels increases with high
525 calcium content, promoting vaterite formation, which is consistent with higher vaterite contents
526 observed in ECC-S specimens [39]. Amorphous CaCO3 forms when the pH value of the pore
527 solution is low, especially in the case of carbonation. But CO2 release from amorphous CaCO3
528 coincides with H2O release from CH, which makes it harder to calculate their masses accurately,
529 especially without a well-defined peak in the TGA/DTG chart [44]. It is important to note that
530 the highest total amounts of CaCO3 were obtained from specimens cured in CO2-water,
531 excluding ECC-FA/CH. Moreover, the highest total amounts of CaCO3 were not always

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532 recorded from specimens subjected to water-based curing (with and without high CO2
533 concentration), which was reported to be the most beneficial type of further environmental
534 conditioning for effective self-healing. In addition, for almost all further curing conditions, the
535 highest CaCO3 contents were found in ECC-S specimens (Fig. 8), although self-healing of cracks
536 (as explained in Section 3.1) was better in other mixtures (ECC-FA, ECC-FA/CH). Therefore,
537 although higher amounts of CaCO3 were obtained mostly from ECC-S, this may not be enough

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538 for complete self-healing, which suggests the importance of tight microcracking.
539 XRD patterns of ECC mixtures in different curing conditions are shown in Fig. 9. Quartz

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540 peaks were significantly more pronounced than peaks for other crystals, regardless of applied
541 curing condition. This was attributed, to a large extent, to the presence of silica sand obtained

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542 during scratching for sample preparation and, to a lesser extent, to the formation of C-S-H and
543 C-A-S-H gels within microcracks. Along with quartz (Q), well-defined peaks of calcite (C),
544 vaterite (V) and aragonite (A) were also observed in XRD analysis. The presence of different

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545 CaCO3 species under CO2-water curing was more pronounced for all mixtures, supporting
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546 previous TGA/DTG findings.
547 Self-healing products formed inside microcracks were also characterized with SEM
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548 micrographs and further analyzed with EDX detector. Fig. 10 shows representative SEM
549 micrographs of different ECC mixtures further cured for 90 days under CO2-water curing beyond
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550 initial 365 days. The figure clearly shows that this type of curing was significantly effective in
551 completely closing microcracks for all mixtures. In all EDX data recorded from different
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552 specimens, Ca peaks reached the highest points, which suggests that the main self-healing
553 products under CO2-water curing in which the highest self-healing performance was achieved
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554 were different calcium carbonate species. However, traces of Si and Al peaks were also observed
555 in ECC-FA and ECC-FA/CH, confirming the formation of C-S-H and slight formation of C-A-S-
556 H gels in the microcracks of these specimens.
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557
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558 4. Conclusions

559 This study investigated autogenous self-healing performance of one-year-old (aged) ECC
560 mixtures with different compositions. ECC mixtures were produced with Class-F fly ash (FA,
561 ECC-FA), Class-F FA with hydrated lime (ECC-FA/CH) and ground granulated blast furnace
562 slag (S, ECC-S). One-year-old specimens were further aged for 90 days under water, air, CO2-
563 water and CO2-air curing, and self-healing assessments were made via crack characterization,
564 electrical impedance (EI) test, rapid chloride permeability (RCP) test and microstructural
565 analysis (TGA-DTG, XRD and SEM). Conclusions drawn from the study are listed below:

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566 • In terms of crack plugging performance and other testing methods, CO2-water curing was
567 the best among all curing conditions, followed by water curing. These findings indicate that
568 water is a must-have component for enhanced autogenous self-healing efficiency. By
569 properly adjusting mixture proportions and selecting further environmental conditioning,
570 widths as large as 458 µm can easily be healed within only 30 days of further curing, despite
571 the very high maturity. Also, a crack healing rate of 100% (from ECC-FA mixture further

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572 cured under CO2-water conditioning) can be achieved within 90 days of further curing,
573 irrespective of different crack characteristics.
• As a new method, EI testing is fast and effective in capturing microcrack occurrence in

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574
575 sound specimens and self-healing in pre-loaded specimens. EI results of sound specimens

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576 from different mixtures increased significantly when microcracks were formed, indicating
577 that crack widths, rather than crack numbers, play an important role in increasing EI results
578 upon pre-loading. Depending on mixture type, further conditioning and subsequent drying of
579
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specimens for EI testing, EI results similar to those of sound specimens can be obtained
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580 from severely damaged specimens, especially ECC-FA. However, EI testing is quite
581 sensitive to changes in pore solution chemistry and moisture state of specimens at the time
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582 of testing.
583 • Compared to EI, RCP testing is less dependent on the ionic states of specimens. One-year
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584 RCP test results of most of ECC specimens (sound and pre-loaded) are either very low (less
585 than 1000 C) or negligible (less than 100 C), in accordance with ASTM C1202.
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586 Microcracking caused marked escalations in RCP test results due to the creation of new
587 paths for free movement of chloride ions. However, even after microcracking – which
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588 caused severe damage – average chloride ion penetrability results of specimens from
589 different mixtures stayed at very low levels. 15 days of further water-based curing
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590 (especially CO2-water) was enough for most pre-loaded specimens to achieve nearly the
591 same RCP test results as sound specimens, suggesting self-healing occurrence.
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592 • Self-healing products formed inside microcracks with CO2-water curing originated mainly
593 from the precipitation of different CaCO3 species, although minor quantities of C-S-H and
594 C-A-S-H gels were also found in the microcracks of some specimens (ECC-FA and ECC-
595 FA/CH). This finding was confirmed with TGA/DTG, XRD analysis and SEM micrographs.
596 Considering the effects of different curing conditions, there appeared to be a difference in
597 the amounts of vaterite in specimens subjected to further water- and air-based curing.

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598 CO2 emissions caused by industrial development, transportation and other industries are at
599 alarming levels nowadays. Although this is widely accepted to be a negative thing, it can also
600 be a very advantageous parameter in terms of autogenous self-healing of microcracks in ECCs.
601 Therefore, using ECC materials in places where CO2 concentrations in the air are particularly
602 high can help reduce those concentrations and significantly contribute to the sustainability of
603 infrastructures through enhanced self-healing capability. The current study also suggests that

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604 along with the high early-age self-healing rate of ECC specimens reported in literature, self-
605 healing rates of aged ECC specimens can be similar to early-age with proper further

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606 environmental conditioning and mixture design.
607
608 Acknowledgement

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609 The authors gratefully acknowledge the financial assistance of the Scientific and Technical
610 Research Council (TUBITAK) of Turkey provided under Project: MAG-112M876 and the

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611 Turkish Academy of Sciences.
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612
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690 30. G. Yıldırım, M. Şahmaran, H.U. Ahmed, Influence of hydrated lime addition on the self-
691 healing capability of high-volume fly ash incorporated cementitious composites, J. Mater.
692 Civil Eng. 27 (2014) 04014187.
693 31. C.A. Clear, The effects of autogenous healing upon the leakage of water through cracks in
694 concrete, Wexham Springs: Cement and Concrete Association, (1985) p. 28.
695 32. M. Şahmaran, İ.Ö. Yaman, Influence of transverse crack width on reinforcement corrosion
696 initiation and propagation in mortar beams, Can. J. Civil Eng. 35 (2008) 236–245.

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697 33. C. Edvardsen, Water permeability and autogenous healing of cracks in concrete, ACI Mater.
698 J. 96 (1999) 448–455.
699 34. C. Aldea, W. Song, J.S. Popovics, S.P. Shah, Extent of healing of cracked normal strength
700 concrete, J. Mater. Civil Eng. 12 (2000) 92–96.
701 35. C. Shi, Effect of mixing proportions of concrete on its electrical conductivity and the rapid
702 chloride permeability test (ASTM C1202 or ASSHTO T277) results, Cem. Concr. Res. 34

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703 (2004) 537-545.
704 36. A.W. Adamson, Physical chemistry, 2nd ed. Orlando, Academic Press, (1973).

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705 37. C. Andrade, Calculation of chloride diffusion coefficients in concrete from ionic migration
706 measurements, Cem. Concr. Res. 23(1993) 724-742.

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707 38. H. Huang, G. Ye, C. Qian, E. Schlangen, Self-healing in cementitious materials: materials,
708 methods and service conditions, Mater. Design 92 (2016) 499-511.
709 39. L. Black, C. Breen, J. Yarwood, K. Garbev, P. Stemmermann, B. Gasharova, Structural

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710 features of C–S–H (I) and its carbonation in air—a Raman spectroscopic study. Part II:
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711 carbonated phases, J. Am. Ceram. Soc. 90 (2007) 908-917.
712 40. P.E. Grattan-Bellew, Microstructural investigation of deteriorated Portland cement
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713 concretes, Constr. Build. Mater. 10 (1996) 3-16.

714 41. W.F. Cole, B. Kroone, Carbon dioxide in hydrated Portland cement, ACI J. Proc. 56 (1960)
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715 1275-1296.
716 42. Z. Sauman, Carbonation of porous concrete and its main binding components, Cem. Concr.
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717 Res. 1 (1971) 645–662.

718 43. G.W. Groves, A. Brough, I.G. Richardson, C.M. Dobson, Progressive changes in the
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719 structure of hardened C3S cement pastes due to carbonation, J. Am. Ceram. Soc. 74 (1991)
720 2891-2896.
721 44. L. Brecevic, Solubility of amorphous calcium carbonate, J. Cryst. Growth 98 (1989) 504–
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722 510.
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725

726

727

728

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729 List of Tables and Figures

730 Table 1 Chemical and physical properties of FA, GGBFS, PC and silica sand.
731 Table 2 Ingredients of different ECC mixtures.
732 Table 3 Characterization of microcracks depending on mixture type and further 90-day
733 environmental conditioning.
734

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735 Fig. 1. Conditioning of sound and pre-loaded specimens in different curing cabinets.
736 Fig. 2. Distributions of microcrack widths created after initial pre-loading of different ECC

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737 mixtures.
738 Fig. 3. Percental self-healing performances of ECC mixtures with respect to different initial

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739 crack widths after 90 days of further curing.
740 Fig. 4. Typical photos of self-healing of cracks with large widths in a limited period of further
741 CO2-water curing.
742
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Fig. 5. Average EI test results of ECC specimens under different curing conditions.
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743 Fig. 6. Evaluation of EIPL/EIS ratio versus rate of crack healing with respect to further curing age
744 (solid lines represent logarithmic trendlines for ratio of EI results, dotted lines represent rate of
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745 crack healing).

746 Fig. 7. Average RCP test results of ECC specimens under different curing conditions.
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747 Fig. 8. Total amount of calcium carbonate calculated using TGA/DTG analysis for ECC
748 mixtures in accordance with different further curing conditions.
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749 Fig. 9. XRD patterns of ECC mixtures in accordance with different further curing conditions.
750 Fig. 10. SEM micrographs with EDX patterns of products in self-healed cracks (taken from CO2-
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751 water cured specimens cured for 90 additional days after 365 days).
752
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755

756

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760 Table 1 Chemical and physical properties of FA, GGBFS, PC and silica sand.
Chemical Composition FA GGBFS PC Silica sand
CaO 3.48 35.09 61.43 0.02
SiO2 60.78 37.55 20.77 99.79
Al2O3 21.68 10.55 5.55 0.06
Fe2O3 5.48 0.28 3.35 0.02
MgO 1.71 7.92 2.49 0.01
SO3 0.34 2.95 2.49 -

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K2O 1.95 1.07 0.77 0.01
Na2O 0.74 0.24 0.19 0.02
Loss on Ignition 1.57 2.79 2.20 0.07

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Physical Properties
Specific Gravity 2.10 2.79 3.06 2.60
2

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Blaine Fineness (m /kg) 269 425 325 -
761

762

763
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Table 2 Ingredients of different ECC mixtures.
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Ingredients, kg/m3
Mixture ID.
PC FA GGBFS CH Water PVA Sand HRWRA
ECC-FA 566 680 - - 331 26 453 5.1
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ECC-FA/CH 539 648 - 62 331 26 453 5.7

ECC-S 593 - 712 - 347 26 474 6.0
764
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765
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766 Table 3 Characterization of microcracks depending on mixture type and further 90-day
767 environmental conditioning.
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Total # of Average rate of

Further Average of Max. CW Average CW
cracks from Max. CW self-healing
Mix ID. curing initial CW* closed after after 90d.
all tested (µm) after 90d.
condition (µm) 90d. (µm) curing, (µm)
specimens curing (%)
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CO2-air 40 112 348 119 74 42

CO2-water 35 138 458 458 0 100
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ECC-FA
Air 26 109 302 121 78 37
Water 34 102 463 99 47 73
CO2-air 38 110 456 69 91 31
ECC- CO2-water 37 134 356 356 17 91
FA/CH Air 28 112 247 64 83 34
Water 38 121 426 80 85 51
CO2-air 37 152 332 - 131 20
CO2-water 28 166 453 386 62 68
ECC-S
Air 37 136 396 39 111 30
Water 29 174 471 397 79 63
768 *CW: Crack width

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4 -RCP
Sound
4 - EI
Air
4 -RCP
Pre-loaded
50±5 oC 4 - EI
Cabinet I 50±5% RH 4 -RCP
Sound
4 - EI
Water
4 -RCP
Pre-loaded

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4 - EI
769

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4 -RCP
Sound
4 - EI
Air
4 -RCP

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50±5 oC Pre-loaded
4 - EI
Cabinet I 50±5% RH
3% CO2 4 -RCP
Sound
4 - EI

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Water
4 -RCP
Pre-loaded
4 - EI
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770
771 Fig. 1. Conditioning of sound and pre-loaded specimens in different curing cabinets.
772
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773
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774
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775
776 Fig. 2. Distributions of microcrack widths created after initial pre-loading of different ECC
777 mixtures.
778

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779 Fig. 3. Percental self-healing performances of ECC mixtures with respect to different initial
780 crack widths after 90 days of further curing.
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781
782
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783
784
785
786
787
788
789
790
791
792
793
794

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365 d. 365+15 d. 365+30 d.
ECC-FA

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ECC-S

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795 Fig. 4. Typical photos of self-healing of cracks with large widths in a limited period of further
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796 CO2-water curing.
797

798
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799
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800
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801

802
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803

804
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805
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806

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807 Fig. 5. Average EI test results of ECC specimens under different curing conditions.
808
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809
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811

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812 Fig. 6. Evaluation of EIPL/EIS ratio versus rate of crack healing with respect to further curing age
813 (solid lines represent logarithmic trendlines for ratio of EI results, dotted lines represent rate of
814 crack healing).
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815
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816

817
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818
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820

821

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822 Fig. 7. Average RCP test results of ECC specimens under different curing conditions.
823
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825
826 Fig. 8. Total amount of calcium carbonate calculated using TGA/DTG analysis for ECC
827 mixtures in accordance with different further curing conditions.

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828
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829
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830 Fig. 9. XRD patterns of ECC mixtures in accordance with different further curing conditions.
831

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Crack Path

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(a) ECC-FA
Crack Path

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(b) ECC-FA/CH
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Crack Path
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C EP
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(c) ECC-S
832 Fig. 10. SEM micrographs with EDX patterns of products in self-healed cracks (taken from CO2-
833 water cured specimens cured for 90 additional days after 365 days).
834

835

836

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