Materials and Design 95 (2016) 422–430

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Materials and Design

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Effective mechanical properties of self-healing cement matrices

with microcapsules
Wenting Li a, Zhengwu Jiang a, Zhenghong Yang a, Haitao Yu b,⁎
a
Key Laboratory of Advanced Civil Engineering Materials (Tongji University), Ministry of Education, Tongji University, Shanghai 201804, China
b
Key Laboratory of Geotechnical and Underground Engineering of Ministry of Education, Tongji University, Shanghai 200092, China

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

Article history: The effective mechanical properties of matrices healed by embedded microcapsules were investigated using
Received 23 September 2015 Eshelby theory based on the microscale healing mechanisms, referring to the mechanical properties of the adhe-
Received in revised form 22 January 2016 sive and the proportion of cracks that could be healed. This was determined by measuring the water absorption
Accepted 26 January 2016
and vacuum saturation of precracked matrices. The microcapsules or cracks should not exceed 4 vol.% to ensure
Available online 28 January 2016
that approx. 90% of the modulus is retained even if the cracks cannot be reattached at all. Both the healed cracks
Keywords:
and unhealed cracks contribute to the anisotropy, with a greater contribution from the unhealed cracks. The elas-
Self-healing tic modulus of the adhesive has a more significant influence on the anisotropy as the applied load increases. The
Microcapsule measured stiffness recovery indicates that the cracks were only partially healed. This value corresponds to a
Effective mechanical properties healing efficiency index of 0.2–0.4 for the present conditions.
Cement-based © 2016 Elsevier Ltd. All rights reserved.

1. Introduction However, improvement of the mechanical performance,

Concrete is one of the most widely used construction materials. Un-
fortunately, it is susceptible to cracking when exposed to certain envi-
ronmental conditions and external loads. This cracking undoubtedly
compromises the performance and potential service life of concrete
structures in terms of their mechanical and/or transport properties [1–9].
Therefore, a bio-inspired self-healing capability has become the focus
of increasing attention because it potentially enables the recovery of the
structural integrity of materials [10–14]. Similar ideas have been incor-
porated to enhance the reliability and sustainability of concrete struc-
tures. Several approaches have been developed based on experimental
explorations to achieve the self-healing of cement-based materials, uti-
lizing bacteria, mineral admixtures, expansive agents, tabulated capsules
or microencapsulation [15–26]. Not surprisingly, the liquid tightness or
the transfer performance of concrete, which initially deteriorated due
to the presence of microcracks, has been shown to be partially or even
completely restored after crack healing by all of the previously men-
tioned strategies because the open paths for liquids can be easily dis-
turbed and/or cut off once the cracks are filled. Accordingly, the healing
efficiency has been mainly related to the recovery of transport properties
because these properties are known to be the major factor affecting the
durabilities of cement-based materials [15–40].
⁎ Corresponding author at: Department of Geotechnical Engineering, Tongji University,
1239 Siping Road, Shanghai, 200092, China. Tel.: +86 21 65982005; fax: + 86 21
65984573.
E-mail address: yuhaitao@tongji.edu.cn (H. Yu).
i.e., rebuilding the transfer of stress between failed faces, is another con-
cern when polymers are used as the adhesive. Polymers can provide fast
recovery of strength compared to other approaches. The restoration of
the load bearing capability, even if only locally on the microscale, should
improve stress redistribution and decrease further openings and the
propagation of existing cracks. This also accounts for the improvement
of the macroscopic mechanical properties in certain states, i.e., the initial
state, and reloading after healing [28,41–45].
The effective or homogenized properties of a composite regard-
ing its microstructure can be theoretically estimated utilizing
micromechanics-based averaging or homogenization techniques in
which the local effects are smeared out on the macroscale. Several
classical theories have been reported in the literature [46–62].
Many of these theories are based on the pioneering work of Eshelby
[48], which provided an estimation of the effective properties of such
composites. Micromechanical solutions have also been employed to
model microencapsulation-based self-healing cement-based com-
posites [63–65]. The effect of the fraction of microcapsules, assumed
to be voids, on the homogenized elastic properties has been numer-
ically evaluated using the representative volume element (RVE), and
the mechanical performance in the initial state and after healing
have been examined using the finite element method (FEM) [63],
with the properties of the damaged elements represented by contin-
uum elements replaced with the properties of the adhesive. Howev-
er, this approach can be more accurate if the elements and the cracks
healed by the adhesive are of the same order of magnitude in size.
Therefore, a more refined mesh is necessary, considering the

http://dx.doi.org/10.1016/j.matdes.2016.01.124
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
 W. Li et al. / Materials and Design 95 (2016) 422–430
microcapsule radius is normally in the micrometer range. However,
this can sharply increase the computational cost. Otherwise, the ef-
fective properties of the matrix after healing should be considered
instead.
A two-dimensional micromechanical damage-healing model has
been proposed for microencapsulation-based self-healing cement-
based materials under tensile loading [64]. The compliance of the
healing matrix has been mainly developed according to the crack
length, which changes with the fracture properties of the phases and
the probability of a crack hitting the capsules. However, the effects of
the mechanical properties of the adhesive on the matrix after healing
have not been considered. Herbst et al. [65] proposed a general model
for local self-healing by applying an adhesive that represents the overall
damage-healing of the crack caused by all physical mechanisms be-
tween healed contacts using the discrete element method (DEM) to dis-
cuss the dependence of the strength of the matrix on the adhesive. For
microencapsulation-based self-healing, the adhesion is in fact mainly
related to the capability of the adhesive to fill the cracks and its mechan-
ical properties. Because it is such a complex process, the healing effi-
ciency depends on many factors including the propagation of cracks to
rupture the wall to release the adhesive, the crack filling mechanism
under capillary action and crosslinking, and other reactions of the adhe-
sive under certain conditions to reattach the open faces. The probability
of a crack hitting the capsules has been discussed extensively because it
is crucial for crack healing to occur [66–68]. Furthermore, the healing ef-
ficiency is supposed to be closely related, first, to the mechanical prop-
erties of each phase and, second, to the filling degree of the cracks by the
adhesive as driven by the capillary effect and to the limited amount of
capsules available in the system. The release of the healing agent from
spherical and cylindrical microcapsules has been numerically investi-
gated using RVE [69]. In particular, Gardner et al. [70] numerically sim-
ulated the capillary flow of cyanoacrylate in discrete cracks in cement
mortar based on the Lucas–Washburn theory. These findings have pro-
vided a good base for the further exploration of the microscale healing
mechanisms.
Indeed, the healing of cracks is a mechanical, physical and chemical
process, as described above. It is noteworthy that the actual healing ef-
ficiency also depends on local fluctuations in the contact conditions and
cannot be described by a simple mathematical expression. Therefore,
the dependence of the effective properties of the matrix on both the me-
chanical properties of the adhesive and the proportion of cracks to be
potentially healed, which has not been reported so far, is specifically
discussed in this paper based on the Eshelby theory, assuming that the
load-induced cracks are randomly and uniformly distributed in the ma-
trix and that the adhesive, as driven by capillary action, only flows into
the load-induced cracks. Moreover, not all of the cracks can be filled and
healed even if the adhesive is sufficiently available because the capillary
force is closely related to the size and connectivity of cracks [71–72],
among other factors. Therefore, the proportion of cracks that can be
healed has been equivalently determined as an input for the analysis
by measuring the absorption resulting from the capillary effect and
the vacuum saturation of the precracked matrix. The stiffness recovery
was measured to validate the analysis.
2. Theoretical estimation of the homogenized elastic properties
The homogenized mechanical properties were estimated by
adopting the well-known Eshelby theory for the inclusion of flat ellip-
soids [48]. The open cracks are characterized as a fictitious material
with zero normal and shear stiffness whereas the mechanical properties
of the healing material can be defined to represent the closed cracks.
The bond between the matrix and the hardened agent is assumed to
be strong enough that no cracking occurs. This is quite important for re-
sistance to the reopening of cracks after healing, which is discussed in
multiscale modeling [Li et al. submitted]. The cracks are all considered
penny-shaped, planar and parallel to the z-direction for simplification,
423
although they may not correspond to the real shapes of cracks in con-
crete that are irregular and have rough surfaces. The overall elastic mod-
ulus and shear modulus of the RVE were estimated assuming a dilute
distribution of cracks. Interactions between the capsules can be
neglected due to the low concentration of the self-healing microcap-
sules, i.e., 1 to 2 wt.%, which ensures that the mechanical properties of
the matrix are not weakened too much by the additional soft phase.
For all estimations, the thickness of the capsule wall is ignored as the
thickness is much smaller than the capsule diameter, and the volume
of the healing agent to be released by a capsule is, therefore, equal to
the capsule volume.
Fig. 1 shows a schematic of the setup of the infinite matrix contain-
ing a few microcapsules, denoted by α, and a typical n-oriented slit
mesocrack (with the normal vector) that coincides with the semi-
principal axes (xβ-direction) of the cracks with a length of 2a0 in a 2-
dimensional domain with the prescribed macrostress σx. The angle be-
tween the xβ-direction and the global coordinate x-axis is denoted by θβ.
The effective elastic stiffness ℂhom for an RVE containing an isotropic
linear elastic matrix and inclusions with the stiffness tensor, ℂs and ℂα,
respectively, is given by [48]
ℂ hom;α ¼ ℂs þ V α ðℂα −ℂs Þ : hAiα ð1Þ
where Vα is the volumetric fraction of microcapsules and Aα is the strain
concentration tensor.〈•〉 is the area average over the RVE.
Assuming the interactions between any inclusions, referring to mi-
crocapsules and mesocracks in the present study, are ignorable, the
ℂhom of the system containing both microcapsules and randomly dis-
tributed cracks can be written as
ℂ hom ¼ ℂs þ V α ðℂα −ℂs Þ : hAiα þ Δℂ f ð2Þ
where the additional overall elastic tensor, Δℂf, due to the presence of a
family of cracks has contributions from both the unhealed and healed
cracks through


Δℂ f ¼ V un ðℂun −ℂs Þ : hAiun þ V h ℂh −ℂs : hAih ð3Þ
with
V f ¼ V un þ V h ð4Þ
where Vf is the volume of the load-induced cracks and is composed of
unhealed and healed cracks, denoted by Vun and Vh, respectively. ℂun
and ℂh are the elastic tensors for unhealed and healed cracks, respec-
tively. For the unhealed cracks, ℂun = 0. For the healed cracks, the com-
ponents of ℂh should be dependent on the properties of the cracks,
i.e., the elastic modulus E and Poisson's ratio ν (or Lamé constants λ
and μ). Several elastic moduli Eh are defined to characterize the cracks
healed by different adhesives, while the Poisson's ratio νh is kept the
same as that of the matrix. An index P is introduced to quantify the com-
bined effects of the probability of a crack hitting the capsules, the chem-
ical nature of the material surfaces to be bonded, etc. P is assumed to
Fig. 1. Orientation of a local crack in an infinite plane with a prescribed stress.
424 W. Li et al. / Materials and Design 95 (2016) 422–430

vary between 0 and 1 to account for open cracks even though the adhe- Therefore, Sun and Sh can be rewritten as [58]
sive is available and cracks are perfectly closed by the adhesive.
Z π=2
Eq. (3) is rewritten as 2
Sun
ijkl ¼ Sβpqrs T βip T βjq T βkr T βls ep ⊗eq ⊗er ⊗es dθβ ð16Þ

 π θcr
Δℂ f ¼ V un ðℂun −ℂs Þ : hAiun þ V h P  ℂh −ℂs : hAih : ð5Þ
Z θcr
2
Shijkl ¼ Sβpqrs T βip T βjq T βkr T βls ep ⊗eq ⊗er ⊗es dθβ : ð17Þ
π 0
hAiα can be related to an (interior point) Eshelby tensor Sα by [48]

−1 The transformation matrix is given by [58]

hAiα ¼ ℂs : ½−Sα : ðℂs −ℂα Þ þ ℂs  : ð6Þ
 
cosθ sinθ
T¼ :
Likewise, hAiun and hAih can be given by − sinθ cosθ

−1
hAiun ¼ ℂs : ½−Sun : ðℂs −ℂun Þ þ ℂs  ð7Þ The components of the Eshelby tensor depend on the crack aspect
ratio c/a0 and can be found in detail in [58].
h
 i−1 Crack healing can only occur if the shell of the capsules can be rup-
hAih ¼ ℂs : −Sh : ℂs −ℂh þ ℂs : ð8Þ tured by the propagating cracks and the released adhesive can fill the
cracks. Therefore, the volumetric fraction of the healed cracks Vh is relat-
Here, the associated Eshelby tensors Sun and Sh should be expressed ed to the two mechanisms through
in global coordinates (x,y) by the transformation tensor T. In the form of
V h ¼ f ðθcr ; γÞ ð18Þ
components for the uniformly distributed mesocracks, it follows that
[58] where γ characterizes the filling ability of the adhesive due to capillary
Z 2π
flow, which is mostly influenced by the crack size, connectivity, etc.
1
Sijkl ¼ Sβpqrs T βip T βjq T βkr T βls ep ⊗eq ⊗er ⊗es dθβ : ð9Þ [71–72], and thus cannot be described by an explicit mathematic formu-
2π 0 la. However, it can be determined by experiments assuming the cracks
are randomly and uniformly distributed in the matrix. This gives the
For a crack to heal, it is essential that the crack can break the walls of volumetric proportion of cracks absorbing adhesive due to capillary
the capsules as it propagates, thereby releasing the embedded adhesive. force with respect to the total volume of cracks, i.e.,
For a crack with the unit normal vector n in an infinite domain with the
prescribed stress σx, as schematically shown in Fig. 1, the stress intensity Vw
γ¼ ð19Þ
factors KI and KII are given by Vf
pffiffiffiffiffiffiffiffi
K I ¼ σ x πa0 cos2 θ ð10Þ where Vw and Vf are the crack volumes determined by absorption and
vacuum saturation, respectively, as reported in the experimental sec-
and tion below.
Eq. (18) becomes
pffiffiffiffiffiffiffiffi
K II ¼ σ x πa0 sinθ cosθ: ð11Þ  
V h θcr Vw
¼ π  : ð20Þ
Vf Vf
In this study, the І-mode fracture is considered to be the dominant
2
fracture mode for the middle section, which is theoretically pure bend-
ing, in the 4-point flexure configuration. The capsule breakage is greatly dependent on the mechanical frac-
The mode-І fracture toughness KIC for a crack to initiate its ture properties of the capsule KαIC, the matrix KsIC, and, most of all, the in-
propagation terface Kint
IC between the capsule and the matrix as described by


K I ≥K IC ð12Þ min K int s α
IC ; K IC ≥K IC : ð21Þ

is determined by
Assuming this precondition is fulfilled in the present study, the
pffiffiffiffiffiffiffiffi healing efficiency is then closely related to the proportion of cracks filled
K IC ¼ σ 0 πa0 ð13Þ
by the adhesive as influenced by both the crack extension and the cap-
where σ0 is the critical stress required to initiate a fracture in the uniax- illary flow.
ial tension configuration, i.e., θ = 0. The parametric study of ℂhom has been performed following
Then, Eq. (18) can be written as Eqs. (2)–(20) and considering the elastic properties of the adhesive as
they relate to ℂβ, the volume of the microcapsules Vα, the total volume
σ0 of the induced cracks Vf, the volume of healed cracks Vh (related to Vw
cos2 θ ≥ : ð14Þ
σx and θcr), the level of load applied σ/σ0 (which determines θcr), and the
healing index P. For this, Vf and Vh (or Vw) need to be known, and they
This gives the critical orientation for the cracks to be activated, de- have been equivalently determined by vacuum saturation and water
noted by θcr, absorption, respectively, as described in the following.

σ0 3. Experimental program
cos2 θcr ¼ : ð15Þ
σr
Cement paste specimens containing microcapsules were used to
Taking advantage of the axial symmetry, the cracks oriented only in verify the theoretical estimations. For comparison, specimens without
[0,θcr] in the first quadrant can be activated to propagate and be poten- microcapsules were prepared to determine the filling capability of the
tially healed. adhesive due to capillary action. In general, the same specimens should
 W. Li et al. / Materials and Design 95 (2016) 422–430 425

Fig. 2. Schematic illustration of the test setup for (a) the 4-point bending test and (b) the water absorption measurements.

be used for all tests. Indeed, the release of the adhesive occurred instan-
taneously once the capsules were broken. Therefore, the specimens
with microcapsules could not be used for the absorption test right
after flexural loading because it takes time for the side surfaces to be-
come sealed prior to the absorption tests [73]. Furthermore, water
was used instead for the absorption tests because the epoxy resin will
lose its flowability over time when exposed to atmosphere although it
has a low viscosity (1.2 × 10−3 Pa·s at 25 °C), which is similar to that
of water. It should be noted that viscosity is not the only factor that af-
fects capillary flow.
3.1. Materials
The poly(styrene-divinylbenzene) (St-DVB) microcapsules were
previously prepared in the laboratory. These capsules enclosed the
epoxy resin (E) that was used as the adhesive to achieve self-healing
[74]. In general, benzylalcohol (BA) was used as the reactive St-DVB dil-
uent. Monomers of styrene (St), divinylbenzene (BPO) and
benzoylperoxide (BP) were the polymerization triggers. Additional sur-
factants, including sodium dodecylbenzene sulfonate (SDBS),
octylphenol ethoxylate (OP-10) and potassium peroxydisulfate (PP),
were also obtained for encapsulation. All of the solvents were of analyt-
ical grade. All of the paste specimens were made with ordinary Portland
cement (Type I) and tap water from the lab.
40 mm × 40 mm × 160 mm were cast and cured under standard condi-
tions (20 °C ± 2 °C, ≥95% RH) until 90 d prior to the test.
3.4. Testing procedures
The flexural strength, denoted by f, was first measured via the
4-point bending test according to ASTM C348 [75]. The remaining spec-
imens were preloaded at a certain level of f, i.e., 0% (intact), 30% and 60%,
respectively, to induce internal cracks. The healed cracks and ruptured
microcapsules were observed to ensure that the preload is high enough
to induce the healing mechanism [74]. Then, the load was removed, and
the specimens were set aside in a room (18–25 °C, 60–70% RH) for 1 d to
allow the healing to occur. The specimens were reloaded the following
day until failure, and the load–displacement curve was recorded for
the initial state and after the healing of the cracks. The reference speci-
mens were grouped into two collections: one for reloading to measure
the mechanical response as described above and the other where the
middle sections (40 mm × 40 mm × 40 mm) were cut for absorption
tests in accordance with ASTM C1585 [73]. After that, the specimens
were dried at 50 °C for 2 d before the vacuum saturation measurements.
A schematic illustration of the test setup is shown in Fig. 2. The cubic
blocks were placed in the container with the sides that experienced
the tensile stressed submerged in water for the water absorption tests.
Overviews of the different tests series are given in Table 1.

3.2. Preparation of microcapsules [74] 4. Results and discussion

The epoxy was first mixed with BA (14 wt.%) in a 250-ml three-neck
round-bottomed flask for dilution. A aqueous surfactant solution of
SDBS (4 wt.%) and OP (4 wt.%) and 2.8 times the amount of epoxy
were added to the flask and mechanically stirred to form a well-
dispersed solution. The solution was gradually heated to 75 °C and
maintained at this temperature for 1 h. While still at this temperature,
the mixture of St, BPO and BP was then added to this solution. Air in
the container was then replaced by argon through an opening in the
flask with the help of a vacuum pump. The temperature was maintained
for 5 h for synthesis. PP (1 wt.%) was then added and allowed to react for
4.1. Experimental results
The water absorbed in volume per exposed surface area versus the
square root of time is plotted in Fig. 3 for two preload levels, i.e., 30%f
and 60%f. The curves can be divided into two distinct stages, i.e., the ini-
tial absorption within the first 6 h and the secondary absorption after
6 h. Not surprisingly, a higher preload led to more absorbed water,
Table 1
Overview of the different flexural loading test series.

3 more hours. In this way, a microcapsule emulsion with a concentra- Description Fraction of Level Number
tion of 30% by mass was obtained. The typical proportion of epoxy microcapsules of of
resin to St-DVB is 9:1 by mass. The microcapsules are 50–500 μm in di- (wt.%) load specimens
(%f)
ameter with the most likely size of 200 μm.
AH0f0 Reference specimens (no 0 0 4a
AH0f30 microcapsules) 0 30 10b
3.3. Preparation of self-healing cement paste containing microcapsules
AH0f60 0 60 10b
AH2f0 Specimens with microcapsules 2 0 4a
Cement paste with 0.42 w/c was used as the host matrix material. Up AH2f30 2 30 10b
to 2 wt.% of microcapsules was added to the cement paste, which is AH2f60 2 60 10b
equivalent to approximately 4 vol.%. Specimens without microcapsules a
For absorption.
were prepared for reference. The prism specimens with dimensions of b
6 for reloading and 4 for absorption.
426 W. Li et al. / Materials and Design 95 (2016) 422–430
Fig. 3. Effect of the applied load on water absorption.
particularly for the secondary absorption. It should be noted that the
polymeric healing agent can flow from the stress-ruptured reservoir
into discrete cracks due to capillary action, followed by polymerization
of the healing agent, which reattaches to the failed surfaces. It usually
requires a certain amount of time for the process to complete. The
epoxy resin used in the present study can solidify within 1 d [74]. Fur-
thermore, the resins released from the capsules preferentially flowed
into the voids with smaller widths because the capillary force increases
with decreasing void radius. Considering the instantaneous and limited
release of the adhesive, only the initial absorption within the first 6 h of
the formation of the cracks was considered as the maximum absorptiv-
ity that the healing agent can achieve. It is noteworthy that part of the
agent will be absorbed by the pores of the matrix; this effect was
taken into account by comparing with the reference, as explained in
the following.
The total void volume was measured with respect to the size of the
specimen using the vacuum saturation technique, as shown in Fig. 4.
The volume of the voids increased with the applied load because more
cracks were induced as the load increased. The void volume includes
both the induced cracks and the initial void volume. For the theoretical
experiment, it is assumed that the initial volume voids remains the
same for all specimens, and thus, the water absorbed by the cracks
can be determined by subtracting the amount of water absorbed by
the reference sample (without the application of an external load)
from the value obtained for the cracked specimens.
Fig. 5 shows the result for the cracks filled within the first 6 h, assum-
ing that the initial void volume remains the same for the specimens
prior to loading. Pre-loading with 30%f and 60%f led to a similar absorp-
tion performance up to 40 s1/2. The specimens pre-loaded with 60%f ex-
hibited a higher absorptivity after that. This result illustrates the
common combined effect of cracks induced by the two levels of load,
i.e., the amount and size, on the absorption at a certain stage. A further
Fig. 4. Relative void volume as determined by the vacuum saturation technique.
Fig. 5. Amount of water absorbed by the induced cracks within the first 6 h.
increase of the load led to the continuous growth of the cracks as well
as the initiation of new cracks. This contributed to a higher absorptivity
over time. An unexpected decrease in the amount of absorbed water
was observed in the interval from 40 to 60 s1/2. This can possibly be at-
tributed to a deviation in the initial void volume from that of the refer-
ence. Further work is in progress to better understand this result.
Table 2 summarizes the volumetric fraction of the added cracks as
determined after 6 h of water absorption and using the vacuum satura-
tion technique for analysis. The difference between the two results is
considered to be the volume of the unhealed cracks.
4.2. Theoretical estimation
Table 3 lists the mechanical properties used as input parameters for
the analysis. Unless stated otherwise, the fracture toughness KIC and the
pffiffiffiffiffi
crack aspect ratio b/a0 are taken as 1:002 MPa  m for plane strain and
0.01, respectively. It should be noted that the size follows a normal dis-
tribution, and the microcapsules with 150–200 μm take a proportion of
approximately 70% by volume, although the full distribution was 50–
500 μm in diameter. A single size (i.e., 200 μm) was used in the model
because the microcapsules with the largest size are supposed to have
the most compromised mechanical properties. Therefore, the analytical
results could provide a lower limit for the mechanical properties of the
matrices, which can be used as criteria in material design.
Adding the microcapsules can influence the mechanical properties
of the matrix material. Fig. 6 shows the normalized Young's modulus
obtained by the theoretical prediction for Vf = 0. The theoretical result
is in good agreement with the experimental result [76] and correctly re-
produces the trend of a diminishing Young's modulus as the volumetric
fraction of the microcapsules increases. According to this result, the mi-
crocapsule content should be below 4 vol.% to ensure that at least 90% of
the Young's modulus of the matrix is retained.
Fig. 7 shows the effect of load-induced cracks on the anisotropy for
Vα = 0. The ratio of the direct stiffness components in the x- and y-
directions, i.e., (ℂhom)22/(ℂhom)11, is plotted versus the applied load
(σ) and normalized to the critical load (σ0), i.e., the load leading to frac-
ture at θ = 0, for the various Young's moduli of the healing agent with
respect to the Young's modulus of the cement matrix, i.e., the Eh/Es
Table 2
Volumetric fraction of induced cracks used as input for the analysis.
Description 30%f 60%f
(Vw) volume obtained after 6 h of water 0.006437 0.011541
absorption (0.016161)a (0.021265)
(Vf) volume by using the vacuum 0.014301 0.024331
saturation (0.035465) (0.045495)
a
The value between the brackets denotes the sum of the cracks and the initial void
space.
 W. Li et al. / Materials and Design 95 (2016) 422–430
Table 3
Mechanical properties of each phase used as input for analysis.
Elastic modulus (MPa) Poisson's ratio
Host matrix 15,000 (Es) 0.25 (νs)
Cracks healed by the adhesive 3080 (Eh) 0.25 (νh)
Unhealed cracks 0 (Eun) 0 (νun)
ratio. The plot exhibits two distinct trends with a remarkable turning
point at σ/σ0 of approximately 1–2. The value of (ℂhom)22/(ℂhom)11 re-
mains one when the applied load does not exceed the critical load be-
cause crack propagation is not initiated. Thus, the specimen remains
in an isotropic state as long as the cracks are randomly oriented.
Both crack generation and healing contribute to the anisotropy of
the material. A sharp increase in (ℂhom)22/(ℂhom)11 can be observed
once σ/σ0 N 1 within a comparatively short range up to a peak value,
followed by its decrease with an increase of σ/σ0. Furthermore, a closer
look at the plot shows that the curves obtained for Eh/Es ≥ 0.4 exhibit a
progressive transition. Eh/Es ≤ 0.3 results in remarkable anisotropy as
demonstrated by the deviation of (ℂhom)22/(ℂhom)11 from one, where
the recovered Young's modulus becomes so insignificant that the
(ℂhom)22/(ℂhom)11 ratio is strongly dependent on σ/σ0. When Eh/Es =
0.4, a critical combination of crack generation and healing is passed, as
indicated by (ℂhom)22/(ℂhom)11 decreasing to approximately one with
σ/σ0 ≥10, beyond which a healing agent with a higher Young's modulus
(Eh/Es ≥ 0.5) contributes to the recovered modulus and anisotropy due
to the increasing mismatch between the Young's moduli of the two
phases.
Fig. 8 shows the effects of crack healing on the anisotropy. The volu-
metric fraction of cracks in the matrix is assumed to be equal to that of
the microcapsules, i.e., Vf = Va, for the case of the maximum healing ca-
pability that is dependent on the amount of healing agent available. One
striking feature is that the healed cracks do not influence (ℂhom)22/
(ℂhom)11 as much as the total cracks, or rather the prehealing cracks,
with increasing Vf. The specimen remains isotropic up to 10% Vf when
all of the cracks are healed, and then, a minor decrease in (ℂhom)22/
(ℂhom)11 can be observed as Vf increases further. The (ℂhom)22/
(ℂhom)11 ratio exhibits a greater change when Vf increases to more
than 5% if only the prehealing cracks are considered.
Fig. 9 shows the bulk modulus and shear modulus normalized to the
corresponding values of the cement matrix, i.e., K/Ks and μ/μs, for the as-
sumed minimum and maximum healing efficiencies, i.e., the cracks ei-
ther remain all open or are all closed. The volumetric fractions of the
cracks and the microcapsules are assumed to be equal. Both the bulk
modulus and the shear modulus cannot be perfectly restored even if
all cracks are healed. As expected, if the cracks remain all open, the me-
chanical characteristics exhibit a certain decrease in value, with the bulk
modulus showing a much greater reduction than the shear modulus. For
Fig. 6. Comparison of the estimated Young's modulus with the corresponding values
obtained from the experiments.
427
Fig. 7. Anisotropic trend changes under the applied load for adhesives with different
mechanical properties.
the healing agent used in the present work, the volumetric fraction of
microcapsules or cracks should not exceed 4 vol.% to ensure that the re-
maining modulus is higher than approx. 90%, even if the cracks cannot
be reattached at all. If the volume of the cracks is higher than that of
the adhesive provided by the capsules, a further decrease of the me-
chanical characteristics will result.
Fig. 10 shows the stiffness normalized to that of the host matrix with
microcapsules only, denoted by (Chom)11/(Chom,α)11, for various healing
efficiency ratios. It shows the upper and lower bounds of (Chom)11/
(Chom,α)11, which correspond to P = 1 and P = 0, respectively. The em-
bedded plot on the right shows the healing index corresponding to the
maximum healing efficiency, where the maximum volume of the
healing cracks should not exceed the volume of the available adhesive,
which is equivalent to the volume of the added microcapsules,
i.e., 4 vol.% (Va), because the simulation of the thickness of the capsule
wall is ignored. Thus, the healing volume is kept at 4 vol.% when the vol-
ume of cracks exceeds that of microcapsules, i.e., for Vf N Va. The same
assumption is made for P = 0.7, where the volume of the cracks is
more than that of the microcapsules as the total volume of cracks in-
creases to approximately 6 vol.%, beyond which the upper bound should
be considered a limit of the restored Young's modulus instead of its lin-
ear extension as highlighted by the green dashed line in Fig. 10.
The (Chom)11/(Chom , α)11 ratio estimated according to the filling de-
gree, which is determined by measuring the water absorption and vac-
uum saturation and listed in Table 2, agrees well with the stiffness
recovery obtained experimentally with a certain standard deviation as
marked by the error bar. Furthermore, the results, as determined either
theoretically or experimentally, are close to the values obtained for P =
0.4 and 0.2, highlighted by the red dashed line and the blue dashed line,
respectively. This indicates that the induced cracks were only partially
Fig. 8. Anisotropic trend as a function of the number of cracks for different healing
conditions.
428 W. Li et al. / Materials and Design 95 (2016) 422–430
Fig. 9. Estimated modulus for various assumed healing efficiencies: (a) the bulk modulus, (b) the shear modulus.
healed depending on the limited flow of the healing agent and its me-
chanical properties and corresponding to a healing efficiency P of 0.2–
0.4 for the conditions in the present study.
5. Conclusions
The dependence of the effective properties of microencapsulation-
based self-healing cement matrices on the mechanical properties of
the adhesive and the proportion of the cracks to be healed has been in-
vestigated in this study by employing the Eshelby theory. The propor-
tion of the cracks to be healed, determined by both of the flowability
of the adhesive through capillary action and the total volume of the
load-induced cracks in the system, was determined by measuring the
water absorption and vacuum saturation of precracked specimens.
The stiffness recovery was experimentally determined to validate the
analysis. The following conclusions can be drawn:
1. For the healing agent used in the present work, the microcapsules or
cracks should not exceed 4 vol.% to ensure that approx. 90% of the
modulus remains even if the cracks cannot be reattached at all.
2. Both types of cracks, i.e., healed and unhealed, contribute to the an-
isotropy of the matrix. With an increasing volumetric fraction of
cracks, the healed cracks do not influence the (ℂhom)22/(ℂhom)11
ratio as much as the prehealed cracks.
3. The elastic modulus of the adhesive exhibits a more significant influ-
ence on the anisotropy with increasing σ/σ0. The case where σ/
σ0 ≥ 10 and Eh/Es = 0.4 passes a critical combination of crack genera-
tion and healing.
4. The stiffness estimated using the filling proportion determined by
the absorption and vacuum saturation measurements is in good
agreement with that determined by the experiments. This result
Fig. 10. Comparison of the estimated stiffness with the experimental values.
indicates that the cracks were partially healed depending on the lim-
ited flow of the healing agent and its mechanical properties and cor-
responding to a healing efficiency index P of 0.2–0.4 for the present
conditions.
Acknowledgments
The authors gratefully acknowledge the financial support provided
by the National Natural Science Foundation of China (51308407,
51208296), the Opening Funds of State Key Laboratory of High Perfor-
mance Civil Engineering Materials (2014CEM009), the Fundamental
Research Funds for the Central Universities (2013KJ095), the Open
Funding of the Key Laboratory of Advanced Civil Engineering Materials
of Jiangsu (CM2014-02), and the National Key Project of Scientific and
Technical Supporting Programs of China (No. 2014BAL03B02).
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