Cement and Concrete Research 73 (2015) 17–24

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Cement and Concrete Research

journal homepage: http://ees.elsevier.com/CEMCON/default.asp

Autogenous healing of marine exposed concrete: Characterization and

quantification through visual crack closure
D. Palin ⁎, V. Wiktor, H.M. Jonkers
Delft University of Technology, Faculty of Civil Engineering & Geosciences, Section of Materials and Environment, Microlab, Stevinweg 1, 2628 CN Delft, The Netherlands

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

Article history: Concrete can autogenously heal cracks potentially increasing construction durability. Studies quantifying this
Received 10 July 2014 process are limited to fresh-water making the controlling parameters in sea-water unclear. Here we visually
Accepted 19 February 2015 quantify the autogenous healing capacity of ordinary Portland cement (OPC) and blast-furnace slag (BFS) cement
Available online 12 March 2015
mortar specimens submerged in fresh- and sea-water. After 56 days, BFS cement specimens in sea-water healed
100% of cracks up to 104 μm, for OPC specimens it was 592 μm. In fresh-water, BFS cement specimens healed
Keywords:
Microcracking [B]
100% of cracks up to 408 μm, while OPC specimens healed 100% of cracks up to 168 μm. Displaying greater healing
Granulated blast-furnace slag [D] efficiency OPC specimens in sea-water became weak, developing unacceptable losses in compressive strength.
Autogenous healing Differences in performance were attributed to the amount of calcium hydroxide in these mortars and specific
ions present in sea-water. Visual crack-healing, therefore, should be assessed in conjunction with a material
functional property.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Many physical and chemical phenomena are usually interdependent
and mutually reinforcing in the deterioration of marine exposed
concrete. Concrete durability is intimately related to the transport
properties of the material, particularly in aqueous environments. Cracks
increase permeability allowing harmful chemicals to penetrate deep
into the concrete, leading to weakening of the cement matrix and
corrosion of the reinforcement. Concrete has a natural or autogenous
ability to heal cracks, greatly reducing chemically driven degradation
phenomena. First reported by the French Academy of Science in 1836,
autogenous healing is principally attributed to the hydration of
unhydrated cement particles and the carbonation of dissolved calcium
hydroxide [1]. Numerous studies have recognised this phenomenon
[2–5], however studies quantifying autogenous healing are scarce
[3,5–7]. Jacobsen et al., [6] found that cracks smaller than 5 μm of
mortar specimens in fresh-water autogenously narrowed in several
locations, but that full crack closure and even crack bridging was less
evident for cracks approximately 10 μm wide. Edvardsen [5] examined
the autogenous healing ability of cracked concrete specimens in fresh-
water through visual observation and permeability. She found that
about 50% of the specimens with crack widths of 200 μm (mean
value) healed completely during 7 weeks of exposure. She also noted
that the greatest healing occurred within the first 3 to 5 days after sub-
mersion. In a later study Reinhardt and Jooss [3] conducted a
permeability test showing a dependence between the initial crack
width, temperature and autogenous healing potential. They showed
that the flow rate of fresh-water through specimens with cracks
50 μm wide incubated at 20, 50 and 80 °C approached zero after
14 days, while for cracks 100 μm wide at 20 °C it was ~5% of the initial
flow, and those 150 μm wide it was ~15%. Gagné and Argouges, [7] re-
cently observed through air-flow measurements that mortar specimens
under 100% relative humidity healed fine cracks (50 μm) 5–10 μm per
month, cracks N 200 μm 15–30 μm per month and cracks N 300 μm
less than 20% after 5 months. Research quantifying autogenous
healing has been restricted to fresh-water and humidity studies,
while the results of these studies suggest that even cracks 10 μm
wide do not always heal and what is meant by healing is not always
clear. Sea-water contains a number of aggressive agents which may
seriously compromise concrete durability. Magnesium, sulfate and
chloride ions, and carbon dioxide are particularly known to attack
the calcium hydroxide, calcium monosulfoaluminate hydrate and
calcium silicate hydrate of hydrated Portland cement. For instance
magnesium-sulfate reacts with calcium hydroxide forming brucite
and gypsum (Eq. (1)), and calcium monosulfoaluminate hydrate
forming ettringite (Eq. (2)) [8]:

⁎ Corresponding author. MgSO4 þ CaðOHÞ2 → MgðOHÞ2 þ CaSO4  2H2 O ð1Þ

E-mail address: d.palin@tudelft.nl (D. Palin). Brucite Gypsum

http://dx.doi.org/10.1016/j.cemconres.2015.02.021
0008-8846/© 2015 Elsevier Ltd. All rights reserved.
18 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24

" # durable concrete. Hydrated BFS cement paste contains less calcium
hydroxide than pure OPC-based cement paste, making the resultant con-
MgSO4 þ CaðOHÞ2 þ CaO  Al2 O3  CaSO4  18H2 O →
Calcium monosulfoaluminate hydrate ð2Þ crete less vulnerable to ionic leaching and subsequent weakening [13].
MgðOHÞ2 þ 3CaO  3CaO  Al2 O3  3CaSO4  32H2 O : Studies have been conducted on the surface layers formed on marine
Brucite Ettringite exposed concrete [14,15]. These mineral layers are markedly different
than those formed in fresh-water environments. First a brucite layer is
Magnesium chloride reacts with calcium hydroxide forming brucite formed (Eqs. (1)–(3)), which is later overlaid by aragonite (Eq. (4)).
and calcium chloride (Eq. (3)): Precipitation of aragonite over calcite (the more thermodynamically
stable of the two calcium carbonate polymorphs) occurs as a result of
MgCl2 þ CaðOHÞ2 → MgðOHÞ2 þ CaCl2 : ð3Þ magnesium ions present in the sea-water [16]. Conjeaud [14] in his
Brucite Calcium chloride
study observed brucite as a layer on the surface of the mortar specimens
Dissolved carbon dioxide reacts with calcium hydroxide forming after two days of exposure (earliest test age). Those brucite layers
calcium carbonate (Eq. (4)): formed on OPC mortar specimens varied in thickness from sample to
sample and face to face, but on average were about 20 to 50 μm thick.
CO2 þ CaðOHÞ2 → CaCO3 þH2 O ð4Þ Brucite layers formed on Type V (sulfate resistant) cement mortar
Calcium carbonate specimens from the same study were thinner, which was attributed to
reduced calcium hydroxide present in those specimens. Overlaying
and calcium bicarbonate upon reaction with calcium carbonate these brucite layers was a thicker, but more slowly developing layer of
(Eq. (5)): aragonite. Following two years of exposure the thickness of this
aragonite layer reached a thickness of 300 μm for all cement types
CaCO3 þ H2 O þ CO2 → CaðHCO3 Þ2 ð5Þ
Calcium bicarbonate tested. Conjeaud concluded that the brucite–aragonite double layer,
formed at the expense of the cement matrix, served as a protective
and gypsum upon reaction with calcium hydroxide and calcium skin suppressing further attack of the mortar matrix. Given their
monosulfoaluminate hydrate (Eq. (6)): potential one might wonder to what extent these minerals contribute
" # to the autogenous crack healing capacity of concrete in the marine
environment.
CO2 þ CaðOHÞ2 þ CaO  Al2 O3  CaSO4  18H2 O →
Calcium monosulfoaluminate hydrate ð6Þ Specific ions present in sea-water, which on the one hand may afford
3CaO  Al2 O3  CaCO3  xH2 O þ CaSO4  2H2 O : marine concrete with a certain crack healing potential, on the other,
Gypsum may also be responsible for reductions in material functionality. Quanti-
tative data on the crack healing capacity of marine exposed concrete is
Gypsum, calcium chloride and calcium bicarbonate are soluble in still largely missing, while the link between healing and material
sea-water and therefore easily leached from concrete, resulting in in- functional properties such as strength is not clear. The aim of the current
creased porosity, permeability and possible reductions in mechanical study is to quantify autogenous healing of concrete in relation to
strength [9,10]. Although the sulfate concentration in sea-water is material strength and in so doing is the first to reconcile these aspects.
high enough for ettringite formation (Eq. (2)), the expansive nature of Furthermore, we define: (1) healing as the complete visual crack
the ettringite formed is reduced by the presence of chloride [10]. In ac- closure at a specific (crack width) location; (2) crack narrowing as a
cordance with Eqs. (1)–(3), brucite formation continues until calcium reduction of a crack width at a specific location and; (3) healing efficiency
hydroxide is sufficiently depleted. Following this, magnesium sulfate as the percentage of healed cracks up to a specific crack width.
is then able to decalcify the calcium silicate hydrate (the binding mate-
rial of the cement) transforming it to magnesium silicate hydrate a non- 2. Experimental programme
cementitious material. This reaction can be illustrated as follows
(Eq. (7)) [11]: To characterize and quantify the autogenous healing ability of
submerged mortar specimens, four series were set up: (1) OPC-based
xCaO  SiO2  kH2 O þ xMgSO4 þ mH2 O→ ! specimens in fresh-water; (2) BFS cement specimens in fresh-water;
ð7Þ (3) OPC specimens in sea-water; and (4) BFS cement specimens in
yMgO  SiO2  nH2 O þ ðx−yÞMgðOHÞ2 þ x CaSO4  2H2 O
Gypsum sea-water. Two specimen geometries were employed, cube specimens
were analysed for compressive strength development and cracked
where k þ m ¼ n þ 3x−y: prisms to quantify visual crack closure.

Conversion of calcium silicate hydrate to magnesium silicate hydrate 2.1. Sample preparation
is known to result in weakening of the cement matrix [9–11].
Chemical vulnerability of marine exposed concrete may be Cubes (40 mm) and prisms (40 × 40 × 160 mm) were cast from OPC
compounded by physical stress. Cracks generated through cycles of (CEM I 42.5 N, ENCI, The Netherlands) and BFS cement (CEM III/B 42.5 N
heating and cooling, wetting and drying, and corrosion of the reinforc-
ing steel greatly increase concrete permeability. Of these, cracks due Table 1
to corrosion of the steel reinforcement are the most destructive. Con- Mix-design for mortar specimens.
crete steel reinforcement develops a passive layer, which, while intact Amount [kg/m3]
protects the steel from corrosion. Chloride ions present in sea-water,
Constituent CEM I 42.5 N CEM III/B 42.5 N LH
however, may destroy this passive layer allowing reinforcing steel in
oxygenated areas to oxidize. Oxidation may be accompanied by consid- Cement 507 494
Water 253 247
erable volume increase causing expansive pressure, cracking and even-
Water cement ratio 0.5 0.5
tual weakening of the concrete matrix [12]. The addition of specific Sand fraction (mm)
supplementary cementing materials to Portland cement are known to 1–2 608 608
increase the resistance of concrete to marine based chemical attack 0.5–1 426 426
[12]. Blast-furnace slag (BFS), a product of the steel industry greatly 0.25–0.5 167 167
0.125–0.25 319 319
reduces concrete porosity leading to a less permeable and hence more
 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24
Table 2
Synthetic sea-water composition based after the major constit-
uents of sea-water [18].
Compound Amount [g/l]
NaHCO3 0.19
CaCl2·2H2O 1.47
MgCl2·6H2O 10.57
Na2SO4·10H2O 9.02
KCl 0.75
NaCl 24.08
LH, ENCI) in accordance with EN 1015-11 [17]. The applied mix design is
shown in Table 1. Prism specimens were reinforced with a 4 mm
threaded steel bar, which was placed in the centre and parallel to the
horizontal axis so that the bar protruded ~30 mm from out the mould.
Cubes and prisms were carefully removed from their moulds after
24 h, tightly sealed in polyethylene plastic bags and kept at room tem-
perature for a total curing period of 28 days. Following curing, prism
specimens containing the steel reinforcement were stretched by a
displacement-controlled load resulting in the formation of multiple
cracks. Cracks up to 1 mm were formed.
2.2. Autogenous healing incubation conditions
Two sets of plastic buckets were prepared, the first set containing 4 l
of tap-water and the second 4 l of synthetic sea-water (20 ± 2 °C). Tap
water and synthetic sea-water are to be called fresh-water and
sea-water respectively for the remainder of the text. The sea-water
was produced from technical grade chemicals (Sigma-Aldrich), and
the composition of which is shown in Table 2. Three cubes or one
cracked prism was submerged in each bucket. The pH of the water
was recorded before being changed every two weeks. Water was
changed to mimic in situ conditions and prevent ion depletion. The
buckets were kept open to the atmosphere during the experiment to
allow for gas diffusion across the water–air interface.
2.3. Precipitate characterization
An environmental scanning electron microscope (ESEM) (Philips XL
30 ESEM, Eindhoven, The Netherlands) was used to study the surface of
the cubes before and after submersion for 56 and 140 days. Prior to
Fig. 1. ESEM images were taken at a 250× magnification of: (A) CEM I-based specimens in fresh-water; (B) CEM III/B in fresh-water; (C) CEM I in sea-water; and (D) CEM III/B in sea-water,
after 56 days submersion.
19
analysis submerged cubes were removed from the water and air-
dried. Cubes submerged for 140 days were also impregnated with
epoxy and polished sections prepared for elemental mapping through
energy dispersive spectroscopy (EDS) (EDAX, Philips, Eindhoven, The
Netherlands). The surface composition of the cubes was chemically
characterized by Fourier transform infrared spectroscopy (FTIR) (Spec-
trum 100, Perkin-Elmer Inc., United States of America). Samples
(b 5 mg) were prepared by scraping the dry surface of the cubes before
and after 56 and 140 days of submersion. Spectra were the result of 32
scans with a resolution of 4 cm−1 in the range of 4000–600 cm−1.
2.4. Strength development
The compressive strength of the mortar cubes was determined on a
Servo-Plus compression test machine and Cyber-Plus evolution control
unit (Matest, Italy) at a rate of 1 MPa/s, 2, 7, 28, 84 and 168 days after
casting. Unsubmerged OPC and BFS cement cubes were kept in sealed
plastic bags to test for any difference between their compressive
strength and that of submerged specimens. The values reported are
the average of three specimens.
2.5. Quantification of crack-healing
Cracks were randomly selected from the cracked prisms from each
series. Visual crack closure was assessed through stereomicroscopic ob-
servation (Leica MZ6, Germany), photographic imaging (Leica applica-
tion suite 4.0, Germany) and measurement (InDesign, Adobe Systems
Incorporated, United States of America). Crack widths perpendicular
to two opposing crack faces were measured at 1 mm intervals for
10 mm from each specimen edge. To follow visual crack closure over
time these locations were monitored every two weeks. The crack
healing percentage was calculated according to Eq. (8) [19]:
Cwi −Cwt
Visual crack closure ¼  100 ð8Þ
Cwi
where Cwi is the initial crack width and Cwt is the width measured at
time t.
20 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24

Fig. 2. ESEM/EDS analysis of polished sections prepared 140 days after submersion. ESEM images showing: (A) CEM I-based specimens after submersion in fresh-water; (C) CEM III/B in
fresh-water; (E) CEM I in sea-water; and (G) CEM III/B in sea-water. EDS analysis of: (B) CEM I in fresh-water; (D) CEM III/B in fresh-water; (F) CEM I in sea-water; and (H) CEM III/B in sea-
water. Yellow in the EDS images represents calcium while blue represents magnesium.

3. Results 3.2. Analysis of polished sections

3.1. Microscopy study of surface precipitates
ESEM analysis of precipitates formed on the surface of the speci-
mens revealed a striking difference between those submerged in
fresh-water (Fig. 1A and B) and those submerged in sea-water
(Fig. 1C and D). Fresh-water submerged specimens formed a layer
of rhombohedral crystals, while specimens in sea-water were
covered in a billowing layer of needles. Rhombohedral crystals may
be associated with calcite, and needles with aragonite [20]. Precipi-
tation for the series tested seemed to have ceased after 56 days
submersion.
ESEM/EDS analysis of the CEM I cube specimens in fresh-water
displayed a layer ~ 10 μm thick on their surface (Fig. 2A and B), while
CEM III/B specimens formed a layer ~5 μm thick (Fig. 2C and D). These
layers were an association of calcium, oxygen and carbon suggesting
them to be calcium carbonate (Eq. (4)). CEM I and CEM III/B specimens
submerged in sea-water formed a double skin on their surface. The high
magnesium concentrated or lower layer, likely brucite (Eqs. (1)–(3)),
was precipitated immediately atop of the specimens, while the outer
layer resembled the elemental composition of those layers formed on
the fresh-water submerged specimens i.e., calcium carbonate. CEM I
specimens formed a lower layer ~ 50 μm thick and the upper was
 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24 21

Table 3
FTIR bands of mineral precipitates present on submerged cube specimens.

CEM I fresh-water CEM III/B CEM I sea-water CEM III/B sea-water

fresh-water
Day

0 56 0 56 0 56 0 56

Wave number [cm−1] Mineral Reference

3643 – 3640 – 3642 – 3642 – Portlandite [Ca(OH)2] [21]

– – – – – 3694 – 3690 Brucite [Mg(OH)2] [21]
1795 1797 – 1797 – 1786 1794 1787 Calcite [CaCO3] [22]
1409 1400 1420 1405 1415 1440 1413 1445
873 872 874 872 – – 874 –
713 713 – 713 – 712 712 712
– – – – – 1083 – 1083 Aragonite [CaCO3] [22]
– – – – – 853 – 854
– – – – – 700,712 695,712 700,712

~150 μm. Below this double skin, the subsurface of the CEM I specimens
submerged in sea-water appeared visibly porous (Fig. 2E and F). CEM
III/B specimens submerged in sea-water also formed a lower layer,
this layer however was far thinner than those layers formed on the
CEM I specimens at ~ 5 μm, while the outer layer was also thinner at
~100 μm (Fig. 2G and H). Below these surface precipitates magnesium
intrusion could be seen ~ 100 μm into the CEM III/B mortar matrix
(Fig. 2H).
3.3. pH of the submersion water
Submersion of the specimens for 28 days in both the fresh- and sea-
water resulted in a pH rise from ~ 8 to ~ 10 likely resulting from ionic
leaching of the cement paste. Following resubmersion (from day 28 to
56) little or no rise in pH was observed suggesting leaching to have
ceased.
3.4. Chemical characterization of surface precipitates
The peak positions of the FTIR spectra are tabulated in Table 3. Bands
at 3642 and 3696 cm−1 correspond to the O–H stretching vibration of
calcium hydroxide and brucite respectively [21]. Calcite has characteris-
tic absorption peaks: C–O asymmetric stretching vibration (v3), C–O out
of plane bending (v2), and C–O planar bending vibration (v4) centred at
1400, 872 and 712 cm−1 respectively. While aragonite has in addition a
characteristic peak stretching vibration (v1) 1083 cm−1 and the bend-
ing vibration (v4) centred at 700 and 712 cm− 1 [22]. Peaks associated
with calcium hydroxide and calcite were present on unsubmerged
CEM I and CEM III/B specimens. Calcium hydroxide peaks disap-
peared after 56 days submersion in fresh- and sea-water. While
peaks associated with brucite (Eq. (1)–(3)) and aragonite (Eq. (4))
appeared for both specimen types after 56 days submersion in
sea-water, with the brucite peaks being less pronounced for the
CEM III/B specimens.

A B C
Healing [%]

D E F
Healing [%]

Fig. 3. Crack healing percentage as a function of the initial crack width for: (A–C) CEM I-based specimens in fresh- and sea-water; and (D–F) CEM III/B in fresh- and sea-water; after (A and
D) 14, (B and E) 28 and (C and F) 56 days submersion. Unbroken and broken vertical lines of the graphs mark 100% visual crack closure (up to the largest crack width) for sea- and fresh-
water submerged specimens respectively.
22 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24
3.5. Visual crack closure
Crack width measurements were made for each series 0, 14, 24 and
56 days after submersion. Quantification of those results is depicted in
Fig. 3. CEM I specimens submerged in fresh-water for 14 days healed
all crack widths up to 69 μm and 37% of all monitored crack widths
(14 locations out of 38) up to the largest crack width of 536 μm
(Fig. 3A). After 28 days submersion all cracks up to 168 μm had healed
and 82% of cracks up to 557 μm (Fig. 3B). After 56 days all cracks up to
168 μm remained healed and 64% of cracks up to 422 μm (Fig. 3C).
CEM III/B specimens submerged in fresh-water for 14 days healed all
crack widths up to 105 μm and 63% of cracks up to 274 μm (Fig. 3D).
After 28 days healing up to 267 μm was observed and 92% of cracks up
to 458 μm (Fig. 3E). After 56 days submersion all cracks up to 408 μm
had healed. CEM I specimens submerged in sea-water for 14 days had
healed all cracks up to 521 μm and 97% of those up to 601 μm
(Fig. 3A). By day 28 all cracks up to 592 μm had healed and 85% of
those up to 734 μm (Fig. 3B). From day 28 to 56 healing remained un-
changed (Fig. 3C). CEM III/B specimens submerged in sea-water for
14 days had healed all crack widths up to 80 μm and 62% up to
431 μm (Fig. 3D). Healing did not change from day 14 to day 28
(Fig. 3E). By day 56 all cracks up to 104 μm had healed, while 62% of
cracks up to 431 μm remained healed (Fig. 3F). Fig. 5 shows one crack
out of the four chosen from each series presented in Fig. 3. Obvious
differences can be seen between each series, but most noticeable is
the difference in speed of healing between the fresh- and sea-water
submerged specimens. Sea-water submerged specimens healed cracks
twice as fast as those in fresh-water. While CEM I specimens displaying
visibly more precipitate than the CEM III/B specimens in both fresh- and
sea-water. Fig. 4 shows the maximum crack width for 100% healing over
time. CEM I specimens in sea-water displayed the greatest healing
efficiency, considerably less were CEM III/B and CEM I specimens in
fresh-water, while the lowest were CEM III/B cement specimens in
sea-water.
3.6. Strength development
Fig. 6 shows the compressive strength of mortar cubes over time. Be-
fore submersion CEM I specimens began with somewhat higher com-
pressive strengths than CEM III/B specimens, and these roles were
reversed by day 28 with CEM III/B specimens having slightly higher
compressive strengths than CEM I specimens. 28 days after casting
specimens were submerged in either fresh- or sea-water. From day 28
to 168 the mean compressive strength of CEM I and CEM III/B speci-
mens submerged in fresh-water stabilised at 55–60 MPa, with CEM I
Fig. 4. Maximum crack width for 100% healing over time.
specimens having a standard deviation 22 MPa. Specimens submerged
in sea-water however showed a markedly different tendency. The
mean compressive strength of CEM III/B specimens submerged in sea-
water stabilised much like those in fresh-water at ~60 MPa, while the
strength of CEM I specimens in sea-water decreased from day 28 to
168 from 55 to 45–50 MPa a drop of more than 10%. Unsubmerged
CEM I specimens maintained a compressive strength of about 55 MPa.
4. Discussion
We have investigated the autogenous healing ability of CEM I and
CEM III/B mortar specimens submerged in fresh- and sea-water. CEM I
specimens submerged in sea-water displayed the greatest healing
efficiency, somewhat lower were CEM III/B and CEM I specimens in
fresh-water and the lowest were CEM III/B specimens in sea-water.
Differences in healing and degradation phenomena may be attributed
to the presence of specific sea-water ions and calcium hydroxide concen-
trations of the mortars tested. Indeed, sea-water contains calcium,
carbonate, and magnesium ions which may precipitate as minerals.
These precipitates give cementitious materials in sea-water a greater
healing potential over those in fresh-water. Mortar specimens sub-
merged in sea-water formed a brucite–aragonite layer (Eq. (1)–(4))
(Table 3). The sea-water provides the carbonate and magnesium ions
while the mortar supplies the hydroxide and most of the calcium ions.
CEM III/B cement has ~75% less calcium hydroxide than CEM I cement
leaving CEM III/B mortar specimens with significantly lower healing ca-
pacity. Indeed, after 56 days, CEM III/B mortar specimens in sea-water
healed 100% of cracks up to 104 μm while this value was more than 5
times higher for CEM I specimens which healed 100% of cracks up to
592 μm (Figs. 3 and 4). Furthermore, most of the healing for both CEM I
and CEM III/B specimens submerged in sea-water occurred during the
first 14 days (Figs. 2–5). Interestingly, though CEM I specimens sub-
merged in sea-water formed the thickest layers (Fig. 2) and displayed
the greatest healing efficiency of the series tested (Figs. 3 and 4), they
also experienced drastic drops in compressive strength (Fig. 6B). This
loss in structural integrity may be due to the dissolution of calcium
hydroxide, which once depleted opens the way for calcium of calcium
silicate hydrate to be replaced by magnesium forming magnesium silicate
hydrate. Porosity and substitution of calcium silicate hydrate for
magnesium silicate hydrate are known to reduce the strength of marine
exposed concrete [9–11].
Contrary to sea-water, fresh-water contains low levels of ions.
Carbonate ions are present in limited amounts while calcium and mag-
nesium ions are negligible, making calcium carbonate the main mineral
formed during autogenous healing in fresh-water (Eq. (4)). Indeed, the
mortar specimens submerged in fresh-water formed a single layer of
calcite (Fig. 2) (Table 3). Here, more than calcium from the mortar spec-
imens, it is the amount of carbonate ions in the fresh-water, which
limits calcium carbonate precipitation. This was shown by comparable
healing efficiencies of CEM I and CEM III/B specimens submerged for
14 days in fresh-water, even though CEM I contains more calcium hy-
droxide than CEM III/B. In fact, CEM I specimens healed 100% of cracks
up to 69 μm and CEM III/B up to 105 μm. However, after 56 days of sub-
mersion in fresh-water, CEM III/B mortar specimens healed 100% of
cracks up to 408 μm while CEM I specimens healed 100% of cracks up
to 168 μm (Figs. 3 and 4). Healing displayed in this study by CEM I mor-
tar specimens submerged in fresh-water for 56 days is in good agree-
ment with those presented by Edvardsen [5]. The absence of a dense
brucite–aragonite layer on the surface of the fresh-water submerged
specimens likely allows prolonged leaching of calcium ions over the
sea-water submerged specimens, and explains why healing for fresh-
water specimens was seen beyond day 14. The part of dissolved calcium
hydroxide, which was not precipitated as calcium carbonate likely
spreads into the bulk fresh-water where it is re-precipitated. Contrary
to CEM I mortar specimens, for which crack-healing stopped after
28 days, CEM III/B mortar specimens continued to display crack-
 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24 23

Fig. 5. Stereomicroscopic images of cracked specimens: (A–C) CEM I-based specimens in fresh-water; (D–F) CEM III/B in fresh-water; (G–I) CEM I in sea-water; and (J–L) CEM III/B in sea-
water, (A, D, G and J) 0, (B, E, H and K) 28 and (C, F, I and L) 56 days after submersion. Each crack makes up one of the four cracks from each series presented in Fig. 3.

healing until day 56. This steady increase in visual crack closure by the
CEM III/B specimens in fresh-water likely results from the steady
leaching of ions as a result of the fine pore structure and pozzolanic
reactions associated with BFS cement pastes [23]. In addition, besides
limited availability of carbonate ions in fresh-water, variations in the
speed of visual crack closure between fresh- and sea-water may also
be attributed to precipitation rates, as calcite in fresh-water precipitates
slower than aragonite in sea-water [24]. Finally, CEM I and CEM III/B
mortar specimens submerged in fresh-water did not display significant
increases or drops in their mean compressive strengths. Strength in-
creases as a result of further hydration for specimens with such high
water to cement ratios are thought to be negligible. The results of CEM
I specimens did, however, display considerable scatter showing that
fresh-water submerged specimens may also experience considerable
losses in compressive strength (Fig. 6). Only by having increased
specimen numbers can stronger conclusions be made regarding the com-
pressive strengths of submerged specimens.
5. Conclusion
Here we have quantified the autogenous healing capacity of OPC and
BFS cement mortar specimens submerged in fresh- and sea-water. Of
the series tested OPC specimens submerged in sea-water displayed
the greater healing capacity, considerably less were the OPC and BFS
cement specimens in fresh-water, while the lowest were BFS cement
specimens in sea-water. Though OPC specimens in sea-water displayed
the greatest healing capacity they also experienced unacceptable losses
in compressive strength, while the others did not. Differences in perfor-
mance between the series tested are attributed to the amount of calci-
um hydroxide present in these mortars and specific ions present in
sea-water. We therefore propose that studies looking to quantify
healing of cementitious materials through visual crack closure be
conducted in conjunction with material functional properties such as
strength and permeability. Further it is interesting to investigate to
what extent healing occurs within the cracks of healed specimens and
24 D. Palin et al. / Cement and Concrete Research 73 (2015) 17–24
A B
Fig. 6. Compressive strength development of CEM I- and CEM III/B-based mortar cubes cured in plastic bags up to 28 days and subsequently submerged in (A) fresh- and (B) sea-water.
how this relates to permeability. Moreover, this is the first study to
quantify autogenous healing of cementitious materials submerged in
sea-water, and as such represents a valuable reference from where an
improved autonomous self-healing system can later be developed for
combating crack-induced deterioration of marine exposed concrete.
Acknowledgements
The authors wish to thank Arjan Thijssen for his help when
conducting the ESEM/EDS analysis. While the research leading to these
results has been funded through the European Union Seventh Framework
Programme (FP7/2007–2013) under grant agreement no 290308 —
SheMat.
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