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 Smart Materials and Structures

Smart Mater. Struct. 25 (2016) 084005 (12pp) doi:10.1088/0964-1726/25/8/084005

Sealing of cracks in cement using

microencapsulated sodium silicate
P Giannaros1, A Kanellopoulos and A Al-Tabbaa
Department of Engineering, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ, UK

E-mail: [email protected]

Received 7 December 2015, revised 10 February 2016

Accepted for publication 19 February 2016
Published 15 July 2016

Abstract
Cement-based materials possess an inherent autogenous self-healing capability allowing them to
seal, and potentially heal, microcracks. This can be improved through the addition of
microencapsulated healing agents for autonomic self-healing. The fundamental principle of this
self-healing mechanism is that when cracks propagate in the cementitious matrix, they rupture
the dispersed capsules and their content (cargo material) is released into the crack volume.
Various healing agents have been explored in the literature for their efficacy to recover
mechanical and durability properties in cementitious materials. In these materials, the healing
agents are most commonly encapsulated in macrocontainers (e.g. glass tubes or capsules) and
placed into the material. In this work, microencapsulated sodium silicate in both liquid and solid
form was added to cement specimens. Sodium silicate reacts with the calcium hydroxide in
hydrated cement paste to form calcium-silicate-hydrate gel that fills cracks. The effect of
microcapsule addition on rheological and mechanical properties of cement is reported. It is
observed that the microcapsule addition inhibits compressive strength development in cement
and this is observed through a plateau in strength between 28 and 56 days. The improvement in
crack-sealing for microcapsule-containing specimens is quantified through sorptivity
measurements over a 28 day healing period. After just seven days, the addition of 4%
microcapsules resulted in a reduction in sorptivity of up to 45% when compared to specimens
without any microcapsule addition. A qualitative description of the reaction between the cargo
material and the cementitious matrix is also provided using x-ray diffraction analysis.

Keywords: self-healing, microencapsulation, sodium silicate, autonomic

(Some figures may appear in colour only in the online journal)

Introduction is inevitable due to mechanical actions, environmental actions

or their combination. Although certain sizes (those less than
Measured by tonnage, concrete is the most consumed material 0.40 mm) of microcracks do not necessarily effect the struc-
on the planet. Carbon-dioxide emissions associated with tural integrity of the concrete, they propagate and coalesce
cement production alone constitute around 5% of global CO2 forming larger through cracks that can affect structural
emissions [1]. Concrete is relatively cheap, very versatile and integrity. But, even if microcracks do not coalesce, they still
has high compressive strength. On the other hand, the tensile pose a threat to the structure as they can become the channels
strength and ductility of concrete is limited and, for this that will allow corrosive substances to enter concrete.
reason, steel rebars are used. Cracking of reinforced concrete Steel corrosion can be induced chemically from sulfates,
1
sea water or acids. Steel corrosion results in the formation of
Author to whom any correspondence should be addressed. expansive products, which result in further cracking of the
concrete. In extreme cases this eventually causes spalling, and
Original content from this work may be used under the terms
thus further infiltration as a result of an increase in perme-
of the Creative Commons Attribution 3.0 licence. Any
further distribution of this work must maintain attribution to the author(s) and ability. Complete disintegration of steel rebars or pre-stressed
the title of the work, journal citation and DOI. tendons can then lead to catastrophic structural failure. For

0964-1726/16/084005+12$33.00 1 © 2016 IOP Publishing Ltd Printed in the UK

Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

this reason, it would be beneficial if cracks could be sealed agents [13, 14] as well as crystalline additives [15] have also
when they surface. Currently, acceptable levels of perfor- been used to heal cracks up to 0.4 mm. Specimens with
mance of concrete structures are maintained though costly crystalline additives were found to have a higher pH value
routine inspection and repair. It is estimated that around which would favour calcium carbonate precipitation and
40%–60% of the European construction budget is devoted to provide increased corrosion protection. The addition of SCMs
repair and maintenance of existing structures-a large propor- for improved autogenous healing is not considered autonomic
tion of these being concrete structures [1]. In the UK, the size healing as they are conventionally added into cementitious
of the UK repair industry is in excess of £1 billion [2]. In the materials.
United States alone, the annual cost for repair, protection and Fibre additions have been used to create engineered
strengthening of concrete structures is estimated to be cementitious composites (ECCs). Here, the embedment of
between US $18 billion and US $21 billion [3]. fibres causes a distribution of multiple microcracks with a
Various techniques have been explored to protect the specific width when loaded; as opposed to few very large
steel from these aggressive substances and the potential for cracks that would be observed in conventional concrete. This
corrosion. They include surface waterproofing, epoxy coated limitation of crack width allows the cementitious material to
reinforcement, stainless steel reinforcement, fibre-reinforced heal autogenously. Several researchers have explored auto-
plastic reinforcement and cathodic protection. However, none genous healing in ECCs in the laboratory [16], in a natural
of these techniques have solved this ongoing problem and all environment [17] as well as in alkaline and chloride envir-
have significant, either technical or economical, limita- onments [18, 19].
tions [4, 5]. Autonomic self-healing differs from autogenous self-
Modern concrete design codes limit acceptable crack healing in that it uses material components that would
widths. Eurocodes limit crack width to 0.40 mm for rein- otherwise not be found in the material [1]. These materials
forced concrete in serviceability limit state [6]. In other can either be added directly into the cementitious mixture or
structure classes, such as those for water retaining structures stored using a carrier material. By utilising these engineered
or high density concrete for nuclear applications, concrete additions, the healing potential and performance are
must be considered impermeable and for this reason crack improved. Dry was first to explore autonomic healing of
width is limited to 0.05–0.20 mm depending on the exposure concrete by encapsulating sealants, adhesives and water-
conditions and tightness class [7]. proofing chemicals into glass tubes [20–22]. The tubes were
Concrete does possess some inherent self-healing cap- placed into the tensile section of concrete specimens. When
ability and is able to seal limited-width micron-sized cracks. cracking occurred, the tubes released their contents and filled
The distinction between sealing and healing is that the latter the crack volume. Various healing agents have since been
provides a recovery in mechanical properties whilst the for- investigated for their efficacy in sealing or healing cracks in
mer is manifested from visual crack-closure or from recovery cementitious materials [23]. Their performance is quantified
in a durability indicator. Various chemical, physical and through a measure in mechanical recovery or a durability
mechanical processes all contribute to autogenous (synon- indicator. More recently, encapsulated minerals have been
ymous with autogenic) self-healing [8]. Hearn and Morley [9] selected for their improved compatibility with the hardened
classified the different autogenous healing mechanisms along cementitious matrix as well as low cost [24]. Silica-based
with their degree of influence. At early age, on-going healing agents, such as sodium silicate, are considered
hydration of cement is mainly responsible for closing cracks. excellent mineral candidates for self-healing of cementitious
In particular, if insufficient mixing of the cementitious mat- materials. Sodium silicate reacts with calcium hydroxide
erial takes place, unhydrated cement nuclei remain dispersed (CH) in the presence of water to form a calcium silicate
within the cementitious matrix. The volume of cement gel hydrate (C–S–H) gel-the main product of cement hydration.
produced from hydration is approximately 2.3 times the ori- The reaction between sodium silicate and calcium hydroxide
ginal cement volume for ordinary Portland cement (OPC) in the presence of water is given as:
[10] and thus can provide effective crack closure. At later age, Na2 SiO3 + Ca (OH)2
the precipitation of calcium carbonate is the main mechanism
+ H2 0  x (CaO ⋅ SiO2 ) H2 O + Na2 O.
contributing to self-healing of cement. Carbonation of cal-
cium hydroxide occurs in the presence of carbon-dioxide. The
maximum width of crack that can be healed by autogenous The conversion of calcium hydroxide (CH) to C–S–H is
means is dependent on many factors including the type and favourable as the presence of CH is detrimental to both the
quantity of cement, the usage and type of supplementary cement’s chemical and mechanical durability. CH is water
cementitious materials (SCMs), the age of concrete, the soluble and susceptible to acid attack. Also, the interfaces
width/length of crack and the healing environment [8]. around CH are typically highly porous, thereby increasing
An enhancement in autogenous healing can be created permeability and decreasing strength [25]. Sodium silicate has
through the use of SCMs such as blast furnace slag (BFS) and already found multiple uses in cementitious materials. For
fly ash (FA) [11, 12]. BFS and FA improve autogenous example, it is used as an alkali-activator in alkali-activated
healing by enhancing further hydration. The reason for this is cements [26]. In concrete, it is used as a setting accelerator
that BFS and FA hydrate slower than cement and thus more and also applied in the form of silicate mineral paint to
unreacted binder materials remain in the matrix. Expansive enhance waterproofing and improve durability [25, 27].

2
Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Huang and Ye [28] added sodium silicate stored in sponge fraction of microcapsules required to achieve a certain level of
that was sealed with wax (5 mm capsule diameter) into ECCs. healing.
The use of a large volume fraction of capsules was more than As researchers are most interested in the self-healing per-
that able to react with the CH in the cementitious matrix. For formance brought about from the addition of microcapsules,
this reason, the residual sodium silicate was observed to there has been limited report on the effect of microcapsule
crystallise. The self-healing efficiency was observed to be addition on mechanical properties. There is also a lack in report
highly dependent on the concentration of sodium silicate. of the effect of microcapsule addition on rheological properties
Formia et al [29] encapsulated sodium silicate in cylindrical of cement paste. In assessing whether an autonomic self-healing
cementitious hollow tubes of various diameters that were system incorporating microcapsules is feasible, it is most
produced by extrusion. It was found that the sodium silicate important to describe the effect that microcapsule addition has
solution was not released from small (2 mm internal diameter) on the initial properties of the cementitious material. If prop-
tubes. The use of larger extruded tubes (7.5 mm internal erties are reduced significantly, and this value falls below that
diameter) however, resulted in significant load and stiffness required for the application, a lower proportion of micro-
recovery even after a second stage of reloading. Kanello- capsules should be used or the selected microcapsules may be
poulos et al [24] explored the efficacy of silica-based healing discarded as unsuitable.
agents using glass vials placed in the tensile section of mortar Microcapsule admixtures are used extensively in the con-
specimens under different healing environments. Cracks struction industry. Common uses include those for air-entrain-
induced by three point bending (3PB) led to release of the ment, temperature control using phase change materials and
encapsulated material and its subsequent reaction with the increased fire-resistance [34]. There are many physical,
cementitious matrix. Results showed the ability of sodium mechanical, environmental, processing and practical require-
silicate to recover sorptivity and gas permeability properties ments for microcapsules used specifically for self-healing of
to values comparable with uncracked specimens. cementitious materials [35]. A vital physical requirement is that
Autonomic self-healing using embedded microcapsules microcapsules they must survive the aggressive mixing process
(capsules less than 1000 μm in diameter) was first developed of concrete. This includes the stresses exerted from the aggre-
gates as well as the mixing equipment. However, they must be
by White et al [30] for polymeric materials. Since then, the
brittle enough so that they rupture when cracks propagate
proposed technology has seen application in other materials
through them. This main requirement has been addressed by
such as metals, ceramics and concrete [31]. The fundamental
using microcapsules that exhibit rubbery and elastic properties
principle of this self-healing mechanism is that when cracks
when hydrated (i.e. during the mixing process) but change to
propagate in the cementitious matrix, they rupture the dis-
brittle glassy behaviour when unhydrated (i.e. when the material
persed capsules and their content (cargo material) is released
is cured) [36].
into the crack volume. In autonomic self-healing concrete via
It is hypothesised that the effect of the addition of sodium-
microencapusulation, the autogenous capability of cement is
silicate-containing microcapsules on cement hydration is two-
enhanced through the addition of microcapsules. Dependent
fold. Firstly, the addition of microcapsules creates spherical
on the self-healing mechanism, this cargo material may react
voids which impede the binding of cement hydration products.
with the cementitious matrix (hydration and carbonation This reduces hydration and thus lowers the amount of heat
products) or the environment (air, CO2, moisture) to form released. Secondly, if any capsules are broken during mixing,
products that seal, or heal, the crack. A couple of researchers the released sodium silicate will accelerate cement hydration.
have added microencapsulated sodium silicate into cementi- The effect of microcapsule addition on the mechanical
tious materials. Pelletier et al [32] added microcapsules to properties of a cementitious material is dependent on multiple
mortar specimens at 2% volumetric fraction. Random variables such as the size of microcapsules, mechanical
microscale cracks were induced and the ability of micro- properties of microcapsules as well as the bond strength
capsule-containing specimens to recover toughness and flex- between the microcapsules and cementitious matrix. If
ural strength after healing was compared with control microcapsules are relatively small compared with the OPC
samples. However, there is a lack of microcapsule char- particle mean size (5–30 μm), it is possible that they enhance
acteristion as well details of the size of cracks healed in durability and mechanical properties by filling pre-existing
specimens. Gilford et al [33] focused mainly on how micro- voids within the cementitious matrix. Larger microcapsules
capsule preparation parameters (temperature, agitation rate, are able to carry larger quantities of healing agent and it has
pH) effect the shell thickness and size of microcapsules. been shown that, at a fixed volume fraction, larger micro-
Microcapsules were added to cylindrical concrete specimens capsules provide increased healing efficiency [37]. If the shell
that were damaged and left to heal for a 48 h period. The material has high strength and stiffness as well as good
addition of microcapsules was found to increase the stiffness bonding properties to the cementitious matrix, then micro-
post-healing to a level higher than that before damage. Both capsule addition may improve properties. Dispersed spherical
reports by Pelletier et al and Gilford et al lack confirmation of particles have been added extensively in particulate-rein-
microcapsule survivability during mixing as well as proof of forced composites to improve both mechanical and physical
release upon cracking. Also, a quantitative description of the properties [38].
reaction between the microencapsulated material and the This aim of this work is to describe the effect of sodium
cementitious matrix is required to determine the volumetric silicate-containing microcapsule addition on the rheological

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Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Table 1. Properties of microcapsules containing sodium silicate.

Name Shell material Cargo material Mean size ∼(μm)

L500 Gelatin-gum Arabic Na2SiO3 (in a liquid solution) 500
T130 Poly-urea Na2SiO3 (solid) 130

L500 microcapsules contain a liquid sodium silicate solution

dispersed in mineral oil and emulsifier. The quantity of sodium
silicate is approximately 42% that of the total encapsulated
material. The T130 microcapsules are manufactured using an
in situ polymerisation technique using poly-urea as shell mat-
erial. A summary of microcapsule properties are given in
table 1. Optical microscope images of the microcapsules can be
seen in figure 1. Microcapsules were observed to swell in water
(the L500 microcapsules more so than the T130 microcapsules)
and return to their original size after drying. They maintained
their structural integrity throughout this period thus retaining the
encapsulated cargo material. Long-term survivability in high
pH (>13) as well as in a calcium chloride solution was
confirmed.

Microcapsule addition to cement paste

Both the L500 and T130 microcapsules were mixed into

cement paste. Microcapsules were added to CEM I 52.5N
cement manufactured to comply with the requirements of BS
EN 197-1. As the L500 microcapsules are dispersed in a
liquid solution, they are extracted using filter paper and a
vacuum pump. When extracted, they are in a hydrated state
and for this reason are unlikely to absorb much water when
added into the cementitious mixture. The T130 microcapsules
are in powdered form and thus added directly to the cemen-
titious mixture.

Isothermal calorimetry for cement hydration

A Calmetrix I-Cal 2000 high precision isothermal calorimeter

compliant with ASTM C1679 was used to measure the heat of
Figure 1. Microscope images of (a) T130 and (b) L500 microcapsules.
hydration of OPC incorporating microcapsule additions.
Microcapsules were added at volumetric fractions (Vf) of 4%
and mechanical properties of cement. The efficacy of micro- to cement paste with a 0.4 water-to-cement (w/c) ratio. Thus,
encapsulated sodium silicate to close cracks and reduce three different mixes were investigated; (1) OPC only, (2)
sorptivity is quantified. Two different microcapsules encap- OPC with 4% L500 microcapsule addition, and (3) OPC with
sulating both liquid and solid sodium silicate are used. A 4% T130 microcapsule addition. The thermostat was set to
qualitative description of the reaction between the cargo 23 °C and left to stabilise for 24 h. Pre-conditioning of the
materials and the cement matrix is also provided. cement powder and water took place for 2 h before being
mixed for one minute using a plastic spoon. The quantities of
cement and water used were 30 g and 12 g respectively and
the mass of microcapsules was 0.4 g. Logging of the heat of
Materials and experimental methods
hydration was then carried out for 48 h. This time was suf-
ficient to obtain the initial setting peak. The peak power is
Microcapsule characterisation
calculated as the maximum power (first peak) minus the
Two different microcapsules used for autonomic self-healing of power during the induction period (first trough). The initial
cementitious materials, L500 and T130, were provided by setting time was then calculated as the time at one-third of the
Lambson Ltd and Thies Technology, Inc. respectively. The peak power.

4
Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 2. Steel wire addition into prismatic specimens to prevent Figure 3. Set-up of three-point bending (3PB) tests for inducing a
complete sample separation. single central crack in cement specimens.

Testing of viscosity using rheometry

A Brookfield DV3T Rheometer was used to measure the

viscosity of mixes. Once again, three different mixes were
investigated; (1) OPC only, (2) OPC with 4% L500 micro-
capsules, and (3) OPC with 4% T130 microcapsules. Samples
were prepared by mixing cement paste for three minutes
before placing 10 ml into the rheometer sample cup. A SC4-
27 spindle was inserted before leaving the sample to settle for
five minutes. After this time, preshearing from 0 to 30 s−1 was
carried out for one minute to erase shear history due to
mixing. The sample was then left for 30 s to stabilise. After
this, a shear stress versus shear rate relationship was obtained
by subjecting the sample to shear rates varying from 8.5 s−1
to 60 s−1 (ramp up) and back down to 8.5 s−1 (ramp down)
[39]. The gradient of the linear regression of the ramp down
portion of the shear stress versus shear rate relationship was
then used to obtain the (plastic) viscosity.
Figure 4. Control of crack width in specimens using a clip gauge.
Testing is automatically terminated once the width reaches 0.3 mm.
Casting and testing procedure

Cube specimens. Cube specimens (40×40×40 mm)

microcapsules at 4% volume (approximately 1.3% by mass of
were cast to quantify the effect of microcapsule addition on
the ultimate compressive strength (UCS) of cement paste. cement). Mixes were prepared in an identical manner to that
Microcapsules were added at volumetric fractions ranging outlined above and six prisms (40×40×160 mm) were
from 0% to 4% in unit intervals to OPC at 0.4 w/c ratio. cast for each of the three mixes. Specimens were cast with a
Sample mixing was carried out using a Kenwood 1500 W 1.6 mm mild steel wire addition (figure 2) into the prisms
food blender. Specimens were compacted using a vibrating compressive section with a cover of 10 mm from the top to
table and then covered with a plastic film to prevent prevent complete sample separation. After 7 days following
evaporation of water. After 24 h, samples were demoulded the date of casting, sample were removed from the water
and submerged in water in a constant temperature immersed environment and a central 3 mm notch was then
environment of 21 °C±1. Four cubes were tested at each induced using a diamond table saw. This was done to ensure
of 7, 14, 28 and 56 days after the day of casting using a cracks initiated in the centre of the specimen during testing.
250 kN servohydraulic testing frame. Samples were mechanically cracked under three-point
bending using an Instron 5567 30 kN static testing frame at
Prismatic specimens. Three different cement mixes were a rate of 0.125 mm s−1 (figure 3). Crack width was controlled
tested all with a water-to-cement ratio of 0.4. The first was a using a clip gauge (figure 4) and testing was terminated
control mixture of cement and water only. The remaining two automatically once the measured width reached 0.3 mm.
mixtures contained the addition of each of the T130 and L500 Optical microscopy images were taken of samples to measure

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Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 5. Schematic illustration of the sorptivity testing procedure.

Cracks are isolated using aluminium tape.

the crack width after unloading and also to monitor areal

crack healing.

Durability testing. Sorptivity tests were carried out using a

short-term one-dimensional experiment. Sorptivity is a
measure of a materials ability to absorb or desorb liquid by
capillarity. Testing procedure was adapted from the RILEM
TC 116-PCD guidelines [40] in order to create a more suitable
testing procedure for cracked specimens. Cracks were isolated
using aluminium tape on the bottom face of specimens to
ensure that absorption only occurs through the crack area
(shown schematically in figure 5). Changes in sample weight Figure 7. A sliced cross section (40×40 mm) of hardened cement
(to 0.1 g precision) due to water suction were recorded over paste containing L500 microcapsules. Release of liquid cargo
4 h and 16 min. The cumulative water absorbed per unit area material is observed throughout the section.
of inflow surface is then related to the sorptivity by [41]:
Mw = S t,
addition. The sodium silicate and microcapsules (2 g) were
where S is the sorptivity coefficient with units g(√min)−1 and added to 10 g of HPC with 5 g of water. Microcapsules were
t is the time in minutes. The sorptivity coefficient (S) was crushed to guarantee release of the encapsulated material
therefore obtained through linear regression of MW and √t. when mixed with the HPC. Mixes were left for seven-days in
Specimens were tested every seven days over a 28 day a petri-dish before being extracted. Samples were ground
healing period. Each week, samples were removed from water using a pestle and mortar and tested using x-ray diffraction
and left to dry for four days before testing. Cracks were also (XRD) analysis scanning at angles ranging between 10° and
observed weekly using a digital microscope to monitor visual 60° using CuKα radiation. A flow chart of the experimental
crack closure. process is given in figure 6.

Microstructural analysis samples. A qualitative description

of the reaction between the cementitious matrix and the Results and discussion
encapsulated material is desired. For this reason, hardened
Portland cement (HPC) paste was ground after seven days of
Microcapsule distribution and release
water-curing and additions of sodium silicate and
microcapsules were added. Four samples were investigated. Sliced cross-sections were taken of the L500-containing
(1) HPC only, (2) HPC with sodium silicate and water specimens using a diamond blade table saw to confirm
addition, (3) HPC with L500 microcapsules and water excellent survivability and distribution of microcapsules
addition, (4) HPC with T130 microcapsules and water across the sample cross section. The microcapsules are large

Figure 6. Flow chart of the preparation of samples for x-ray diffraction (XRD) analysis.

6
Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 9. Initial setting peaks of cement hydration curves for OPC

(black line), OPC with 4% L500 microcapsule addition (blue line)
and OPC with 4% T130 microcapsule addition (red line).

Rheological properties

Viscosity measurements for the three mixes are summarised

in table 2. Values are in agreement with reported values for
cement paste at 0.4 water–cement ratio [42]. It is clear that
viscosity increases with the addition of microcapsules. The
volumetric addition of 4% L500 microcapsules resulted in an
increase in viscosity by 52% whilst addition of T130 micro-
capsules resulted in a 47% increase. The ability of micro-
capsules to absorb water is likely to contribute to this
reduction in workability. As a result, this will reduce the
compressive strength of the hardened cement paste. However,
the effect of microcapsule addition in mortar and concrete is
likely to be less detrimental than that measured in cement
paste.
Profiles of cement hydration obtained using calorimetry
and can be seen in figure 9. Setting time and peak power for
the three mixes is summarised in table 2. The addition of
L500 microcapsules shows a slight reduction in peak power
but almost no change in setting time. The addition of 4%
T130 microcapsules accelerates the initial setting time and
reduces the peak power by 28%. This is not necessarily
caused by the breakage of microcapsules during mixing but
Figure 8. Scanning electron microscope (SEM) images of ruptured (a) rather the shell and cargo material debris within the powder-
L500 and (b) T130 microcapsules embedded in a cementitious matrix. the latter of which accelerates hydration.
enough to be observed visually as seen in figure 7. Rupture of
embedded microcapsules is observed in greater detail using Effect on mechanical properties
scanning electron microscopy (SEM) as observed in figure 8 Once again, the L500 microcapsules were large enough to be
for the both microcapsules. observed with the naked eye. Their survivability and

Table 2. Viscosity, initial setting time and peak power for cement paste containing microcapsule additions.

Mix Viscosity, μ (Pa s) Initial setting time (hh:mm) Peak ower (mW)
OPC 0.2973 04:08 3.67
OPC+4% L500 0.4544 04:04 3.48
OPC+4% T130 0.4370 03:04 2.64

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Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 10. Crushed cement cubes containing 1%–4% volumetric

additions of L500 microcapsules and tested after 56 days.

subsequent rupture upon cracking is observed on the fracture

planes of cube specimens tested for their UCS (figure 10).
Increasing quantities of microcapsules are observed as the
addition increases from 1% to 4%. Figure 11. Compressive (cube) strength of cement containing 1%–
4% addition of (a) T130 and (b) L500 microcapsules tested at 7, 14,
Rheological results presented above suggest a reduction
28 and 56 days.
in compressive strength will be observed for microcapsule-
containing cement paste samples. Compressive strength
results for varying volume fraction of microcapsules is given
Recovery of durability
in figure 11 for the L500 and T130 microcapsule additions. A
decrease in compressive strength becomes increasingly evi- Sorptivity results are summarised in figure 12 for the three
dent at later ages. In particular, it can be seen that the com- different mixes. The capsule-containing specimens reduce the
pressive strength of capsule-containing specimens plateaus sorptivity significantly after short healing periods. The addi-
after 28 days. This is noticed when using both the L500 and tion of 4% T130 microcapsules reduces the sorptivity drasti-
T130 microcapsules. Although the L500 microcapsules are cally by 45% after a seven-day healing period and this
larger, their detrimental effect on compressive strength is less continues to 34% after 28 days of healing. Observation of
than that of the T130 microcapsules. The flexural strength of OPC and capsule-containing samples during testing at 7 days
capsule containing specimens was seen to increase for the can be seen in figure 13. The samples containing L500
T130 containing specimens whilst it reduced slightly for the microcapsules also show improved sealing of cracks. After a
L500 containing samples. After seven-days water curing, 4% seven-day healing period, the addition of 4% volumetric
addition of microcapsules resulted in a 20% increase for fraction of microcapsules reduces the the sorptivity by 15%
T130-containing specimens and a 17% reduction for L500- when compared with the control sample. After a 28 day
containing specimens. Measurements taken on the bottom healing period, the L500 samples absorb slightly more water
face and mid-sample showed average crack widths of than the control samples. This can be explained by the fact
0.09 mm for the control mix, 0.12 mm for the T130-loaded that the dried residual microcapsule shell material within the
specimens and 0.22 mm for the L500-loaded specimens. sample hydrates and absorbs water. This is favourable for two

8
Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 12. Sorptivity of cracked specimens containing L500 (blue line) and T130 (red line) microcapsules at 4% volumetric fraction
compared with cracked cement specimens (black line). Sorptivity measurements are taken over a 28 day healing period.

ruptured capsule facilitates this reaction. Microscopic images

also verify the improved sealing of cracks in capsule-con-
taining specimens as observed in figure 14. The images
suggest that visual crack sealing observations along are not
sufficient to quantify sealing. Instead, a durability indicator
(e.g. permeability, sorptivity) is necessary.
The T130 microcapsules do show superior crack sealing-
indicated by a greater reduction in measured sorptivity values.
However, the T130 microcapsules do contain more encap-
sulated sodium silicate. It makes sense therefore, to hypo-
thesise that the T130 microcapsules will provide better
healing than the L500 microcapsules due to a larger available
quantity of sodium silicate that has the potential to react with
the calcium hydroxide in the cementitious matrix to form C–
S–H. Further investigation is required to determine whether
powdered sodium silicate is preferred to liquid (or dispersed)
sodium silicate for use as a healing agent. On the one hand,
Figure 13. Comparison of water absorbed by cement control samples
the use of liquid sodium silicate allows for better transport
(left) and samples containing 4% T130 microcapsules (right). into the crack plane. However, on the other hand, as the
Testing is after a seven day healing period. samples are cured in water, there is the possibility that some
of the encapsulated liquid diffuses into the water. The pow-
reasons. Firstly, swelling of the microcapsules will contribute dered cargo material is more likely to remain in the residual
to blocking of cracks and avoid fluids from penetrating deeper shell material (and thus within the crack volume) after the
into the matrix. This is vital to protect the steel reinforcement microcapsule shell has been mechanically ruptured. With
within concrete. Secondly, as water is required for the reac- reference to measured crack widths upon loading, the
tion between calcium hydroxide and sodium silicate to pro- recovery in sorptivity for L500-containing specimens is more
duce C–S–H, the retention of water in the vicinity of the impressive considering the cracks in L500 samples are much

9
Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

Figure 14. Cracks observed in (a) cement specimens, (b) cement specimens with 4% volumetric addition of L500 microcapsules and (c)
cement specimens with 4% volumetric addition of T130 microcapsules. Images on the left-hand side show samples after seven days of
healing whilst those on the right-hand side are after a 28 day healing period.

larger than those in T130 samples and significantly larger than semi-crystalised calcium silicate hydrates. C–S–H itself does
the control samples. not show distinct peaks due to its poor crystalline nature.
Calcium hydroxide (CH) peaks (2θ=18.007, 28.671, 34.101
and 47.12) are very distinct in 7 day hardened cement paste
Microstructural analysis
(HPC) XRD (black line, figure 16) as expected. These peaks
Samples with added sodium silicate or crushed microcapsules are still visible after the microcapsule or sodium silicate
(samples 2–4) showed clear binding properties during their additions. However, their intensity has been significantly
extraction after seven days of reaction (figure 15). XRD reduced indicating a consumption of portlandite. XRD ana-
spectra of the four different samples can be seen in figure 16. lysis of HPC mixed with crushed L500 (blue line, figure 16)
Typical Portland cement hydration products can be observed or T130 (red line, figure 16) capsules and water shows similar
including portlandite (calcium hydroxide), ettringite and characteristics to the HPC mixture with sodium silicate (pink

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Smart Mater. Struct. 25 (2016) 084005 P Giannaros et al

the samples with microcapsule or sodium silicate additions. In

this same region, amorphous C–S–H peaks overlap along
with calcite at 29.405. Calcium carbonate formation is due to
the carbonation of calcium hydroxide during water curing.
This peak is observed to be larger in the HPC+sodium
silicate mix and HPC+L500 mix. It is clear that the addition
of sodium silicate (or crushed sodium-silicate containing
microcapsules) leads to a consumption of CH and production
of C–S–H.
Once again, it is worth noting that the L500 microcapules
Figure 15. Samples extracted after a seven day reaction period. (1) contain less sodium silicate than the T130 microcapsules and
HPC only, (2) HPC with sodium silicate and water addition, (3) HPC this is evident when comparing the XRD spectra.
with L500 microcapsules and water addition, (4) HPC with T130
microcapsules and water addition. Samples 2–4 show clear binding
properties.
Conclusion

Two different sodium silicate-containing microcapsules

(T130 and L500) were added to cement paste to quantify the
effect of their addition on rheological and mechanical prop-
erties. The addition of 4% (with respect to cement volume)
microencapsulated sodium silicate was shown to reduce
sorptivity of cracked specimens over a 28 day healing period.
Thus, the efficacy of microencapsulated sodium silicate to
close cracks and provide sealing was quantified. A qualitative
description of the reaction between the cargo material and
cement matrix was also provided. X-ray diffractograms con-
firm the consumption of calcium hydroxide and the produc-
tion of calcium-silicate-hydrate from the reaction of the cargo
material with the cementitious matrix. Future work is focused
on optimising the volumetric fraction of microcapsules and to
determine the quantity required for a certain level of healing.
Quantification and characterisation of the healing products
will then be compared with those obtained from micro-
structural observations in this work.
Figure 16. X-ray diffractogram of hardened cement paste (HPC,
black line), HPC with sodium silicate addition (pink line), HPC with
4% L500 microcapsule addition (blue line) and HPC with 4% T130
microcapsule addition. Acknowledgments

Financial support from the Engineering and Physical Sciences

line, figure 16). The portlandite peaks in the HPC+L500 Research Council (EPSRC) for the first authors’ PhD stu-
mix are the largest of the three mixtures although they are still dentship is gratefully acknowledged. Support from the
significantly smaller than those in the HPC mixture alone. As EPSRC Materials for Life (M4L) project (EP/K026631/1) is
the L500 microcapsules contain a sodium silicate dispersion also gratefully acknowledged. Additional data related to this
in oil, the amount of sodium silicate released will be less than publication is available at the University of Cambridge’s
that released from the T130 microcapsules. It is no surprise institutional data repository here: https://www.repository.
therefore, that the amount of consumed portlandite is less. cam.ac.uk/handle/1810/253547.
The HPC+sodium silicate XRD and HPC+crushed T130
microcapsules are observed to be almost identical. This
affirms the release of the cargo material and its reaction with References
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