Article

Characterization of Enhanced ITZ in Engineered

Polypropylene Fibers for Bond Improvement
Rishabh Bajaj 1 , Boyu Wang 2 and Rishi Gupta 2, *
1 Department of Civil Engineering, National Institute of Technology Rourkela, Odisha 769008, India;
rishabhbajajnitr@gmail.com
2 Department of Civil Engineering, University of Victoria, 3800 Finnerty Road, Victoria, BC V8W 2Y2, Canada;
boyuwang@uvic.ca
* Correspondence: guptar@uvic.ca; Tel.: +1-(250)-721-7033




Received: 15 April 2020; Accepted: 8 May 2020; Published: 11 May 2020


Abstract: The interfacial transition zone (ITZ) is well known to be a zone of high porosity and
lesser strength and is the weak zone in the fiber-reinforced matrix. This study aims to evaluate the
improvement in the bonding between engineered polypropylene fibers and the surrounding mortar
matrix. The improvement was implemented by modifying the ITZ, which develops between the
fibers and the cementitious matrix. Two commercially available repair materials have been used in
this study, Mix M and Mix P. Mix M served as the base material for the prepared fibers, whereas
Mix P is a fiber-reinforced repair mortar and provides a comparison. A total of six types of mixes
have been investigated. The improved bonding is tested by coating the polypropylene fibers with
supplementary cementitious materials (SCM) using an innovative patented concept. In this study,
silica fume and metakaolin are used as the SCM because of their fine size and pozzolanic capacity.
The study involves multiple items of investigation, including mechanical tests such as compressive
strength, direct tensile strength, and three-point bending tests. Energy-dispersive X-ray spectroscopy
(EDS) of the different mixes helped in evaluating and analyzing the ITZ between the fiber and matrix.

Keywords: fiber coating; repair mortar; scanning electron microscopy (SEM); energy-dispersive X-ray
spectroscopy (EDS)

1. Introduction
Fiber-reinforced concrete (FRC) is increasingly being used in the field due to its high toughness and
energy absorption capacity. Early application of FRC can be traced back to the 1960s when randomly
dispersing steel fiber was employed in analogy with traditional steel reinforcing bars [1]. Cement
composites exhibited the general brittle characteristics under failure loads allowing the steel fibers to
bridge the propagating cracks. Steel FRC possesses a long history of successful application [2], whereas
recent research shows a growing interest in synthetic fibers. Synthetic fibers, such as polypropylene
(PP), polyethylene, polyvinyl chloride, and many others [3], have some substantial advantages over
metallic ones. The typical characteristics of synthetic fibers include chemical stability in aggressive
environments, exemption from oxidation, lightness, easy stocking and handling, and electromagnetic
transparency. As a result, they have been used in a variety of places including road pavements [4],
storm sewers, water drains [5], etc.
A major issue associated with using synthetic fibers is caused by their lack of hydrophilicity. They
react very little with the concrete matrix and consequently, loading is hardly transferred from the
matrix to the fibers [1]. Another major challenge is the interfacial transition zone (ITZ). Figure 1 shows
that owing to the “wall effect”, the matrix around macroscopic particles such as aggregates and fibers
does not pack as efficiently as in the rest of the matrix [6,7]. Poor bonding between the aggregates/fibers

J. Compos. Sci. 2020, 4, 53; doi:10.3390/jcs4020053 www.mdpi.com/journal/jcs

J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 2 of 20

shows
J. Compos.that owing
Sci. 2020, 4, 53to
the “wall effect”, the matrix around macroscopic particles such as aggregates 2 of 19
and fibers does not pack as efficiently as in the rest of the matrix [6,7]. Poor bonding between the
aggregates/fibers and the cement matrix generates a weak ITZ [8] that hinders full exploitation of the
and
fiberthe cement[6].
strength matrix generates
To address a weak
these ITZ [8] thatmany
shortcomings, hinders full exploitation
approaches of the
have been fiber strength
investigated. [6].
These
To address these shortcomings,
are described below. many approaches have been investigated. These are described below.

Figure 1.1.Scanning
Figure Scanning electron
electron microscope
microscope (SEM)
(SEM) imageimage showing
showing polypropylene
polypropylene fiber, interfacial
fiber, interfacial transition
transition
zone (ITZ),zone
and (ITZ),
mortar. and mortar.

Surface
Surface treatment
treatmenthas has been considered
been considered one of
onetheofviable techniques
the viable to improve
techniques ITZ. SomeITZ.
to improve treatment
Some
methods
treatmentpreviously
methodsreportedpreviously in thereported
literature include
in the cold plasmainclude
literature treatment [9], mechanical
cold plasma treatmentmicropitting [9],
treatment
mechanical[10], flame treatment
micropitting treatment [11], wetflame
[10], chemical treatment
treatment [11], [12], and nanosilica
wet chemical treatmenttreatment
[12], and[1].
Mechanical micropitting
nanosilica treatment [1]. treatment
Mechanicalinvolves creating
micropitting indentations
treatment involves on the fiber indentations
creating surface by pressing
on the
the
fiberfibers between
surface two hardened
by pressing the fiberssteel surfaces.
between two This method
hardened may
steel cause cross-section
surfaces. This method loss mayand cause is
hard to be applied
cross-section loss andon short
is hardfibers towith small diameters.
be applied on short Wet fiberschemical
with small treatment method
diameters. requires
Wet chemicalthe
use of the method
treatment acid or any otherthe
requires solution
use of the etching
acid ortheanyfiber surface
other suchetching
solution that the thefrictional
fiber surfaceproperties
such that of
fibers are improved.
the frictional properties Thisofmethodfibers can are result in degradation
improved. This method of the canmechanical
result in performance
degradation of of the
fiber if excessive
mechanical etching takes
performance of theplace.
fiber In addition, etching
if excessive disposaltakes of etching
place.chemicals
In addition, causes environmental
disposal of etching
issues.
chemicals Thecauses
problem with flame or
environmental heat treatment
issues. The problem is the
withincrease
flame or in brittleness
heat treatment of theis fiber materials
the increase in
after the treatment.
brittleness of the fiber Compared
materials to after
these the methods,
treatment.cold Compared
plasma treatment to theseis methods,
relatively coldeco-friendly,
plasma
fast, and does
treatment not exhibit
is relatively excessive brittleness.
eco-friendly, fast, and Colddoes plasma
not exhibittreatment
excessivecan reduce the surface
brittleness. energy
Cold plasma
of the polymer surface and thus convert the hydrophobic structure
treatment can reduce the surface energy of the polymer surface and thus convert the hydrophobic of PP surfaces to hydrophilic,
which
structure increases chemicaltobonding
of PP surfaces hydrophilic, with thewhichcementitious matrix [13].
increases chemical bondingHowever,with the the cementitious
cold plasma
method
matrix [13].can still producethe
However, detrimental
cold plasma waste unless can
method somestillspecific
producegas composition
detrimental iswaste selected [9]. Some
unless some
specific gas [14]
researchers composition is selected
have previously used [9].nanosilica
Some researchers
as the coating[14] have previously
to improve the used
bondingnanosilica
between as the
coatingand
matrix to improve
the PP fibers. the bonding
The silicabetween
nanoparticlesthe matrix and theon
are deposited PPPP fibers.
fibersThe silica
via the nanoparticles
rapid acid-catalyzed are
deposited
sol–gel on PP fibers
technique via the
[15]. The userapid acid-catalyzed
of nanoparticles sol–gel technique
is associated [15]. Theinuse
with an increase theofcost
nanoparticles
which could is
associated with
potentially limitan theincrease
applicationin the ofcost
thiswhich could potentially limit the application of this technique.
technique.
Based on
Based on the
the literature
literaturereview,
review,there thereexists
existsa aneed
needtotosurface
surfacetreat
treat thethe fibers
fibers withwith a material
a material thatthat
is
is relatively
relatively eco-friendly
eco-friendly andand lowlow cost.SCMs
cost. SCMssuchsuchasasmetakaolin
metakaolinand andsilica
silicafume
fumeare are considered
considered to to be
sustainable and
sustainable andenvironmental-friendly
environmental-friendly materials.
materials. ThereThere are CO
are limited limited CO2 during
2 emissions emissions during
metakaolin
metakaolin [16,17]
production production [16,17]
and silica fumeandis silica
a waste fume is a waste
material from the material fromprocess
industrial the industrial
[18]. Over process [18].
the years,
Over the
SCMs have years,
beenSCMs used to have
dealbeenwithused to dealITZ
the porous with the porous
[19,20]. ITZ [19,20].
Pozzolans, including Pozzolans,
metakaolin,including
silica
metakaolin,
fume, and flysilica
ash are fume, and fly reactive
chemically ash are chemically
with calcium reactive
hydroxide withincalcium
the concretehydroxide
to form in cementitious
the concrete
to form cementitious
materials, which results materials,
in a denser which ITZ.results in a denser
Physically, using ITZ. Physically,
microfillers suchusing microfillers
as metakaolin andsuch as
silica
fume can also fill up the voids between the reinforcement and matrix. As an example, most researchers
J. J. Compos.Sci.
Compos. Sci.2020,
2020,4,4,53
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3 of

metakaolin and silica fume can also fill up the voids between the reinforcement and matrix. As an
example,
have most that
concluded researchers
silica fumehave concluded
is indeed that silicainfume
instrumental is indeed
enhancing instrumental
concrete propertiesinbyenhancing
improving
concrete
the properties
ITZ [21–23]. by improving
However, SCM, the ITZis
which [21–23]. However,
normally used to SCM, which
replace is normally
cement used
content byto
upreplace
to 20%
cement content by up to 20% volume [24–26], does not clearly target the ITZ.
volume [24–26], does not clearly target the ITZ. Previous studies have proved that the densification Previous studies haveof
proved
ITZ that the
is possible bydensification
coating coarse of aggregates
ITZ is possiblewithby coating
silica fumecoarse aggregates
[21]. Other with silica
researchers fumeshown
[27] have [21].
Other
that theresearchers
addition of[27] have shown
pozzolans such that the addition
as silica fume and offly
pozzolans
ash doessuch helpasinsilica fume and fly ash
the densification does
of the ITZ
help in the densification of the ITZ which, in turn, improves
which, in turn, improves the mechanical strength and durability [27,28]. the mechanical strength and durability
[27,28].
In this study, a novel method to surface treat the PP fibers with SCMs is proposed. The core of this
method Inisthis study,
based on aannovel method
invention by to surface
Gupta treat
titled the PP Treatment
“Surface fibers withfor SCMs is proposed.
Concrete The core [29].
Reinforcement” of
this method is based on an invention by Gupta titled “Surface Treatment
The focus of this research was to investigate the effectiveness of surface-treating fibers for improved for Concrete
Reinforcement”
bond strength. The [29]. The focus
proposed of this research
method was to investigate
utilizes pozzolans including the silica
effectiveness
fume andof surface-treating
metakaolin. The
fibers for improved bond strength. The proposed method utilizes pozzolans including silica fume
presence of such pozzolans is usually expected to improve the strength of the matrix. Instead of adding
and metakaolin. The presence of such pozzolans is usually expected to improve the strength of the
to the entire mix, these pozzolans targeted only in the regions requiring their use in ITZs surrounding
matrix. Instead of adding to the entire mix, these pozzolans targeted only in the regions requiring
the fibers [29]. To achieve this, a new method is developed which disperses the PP fibers, applies
their use in ITZs surrounding the fibers [29]. To achieve this, a new method is developed which
adhesive to every fiber, and adheres pozzolans to the fibers (Figure 2). In addition, one commercially
disperses the PP fibers, applies adhesive to every fiber, and adheres pozzolans to the fibers (Figure
available repair material is used as the base material where the surface-treated fibers are added. Repair
2). In addition, one commercially available repair material is used as the base material where the
materials are now widely used to extend the lifetime of structures and thus have a greater need for
surface-treated fibers are added. Repair materials are now widely used to extend the lifetime of
maintaining the safety and serviceability [30]. Most of these repair materials comprise a component
structures and thus have a greater need for maintaining the safety and serviceability [30]. Most of
of cement, polymer, and at times, both [30–32]. The base material in this study is classified as a
these repair materials comprise a component of cement, polymer, and at times, both [30–32]. The base
cementitious
material in this repair mortar.
study is classified as a cementitious repair mortar.

Figure 2. Schematic diagram of the proposed method of improvement of ITZ.

Figure 2. Schematic diagram of the proposed method of improvement of ITZ.
2. Materials and Methods
2. Materials and Methods
2.1. Materials
2.1. Materials
In this study, polypropylene fibers are treated with two SCMs to produce engineered surface-treated
fibers In this study,
(ESTF) of twopolypropylene fibers are treated
kinds: silica fume-coated and with two SCMs to produce
metakaolin-coated engineered
fibers. Since surface-
silica fume has
treated fibers (ESTF) of two kinds: silica fume-coated and metakaolin-coated fibers.
a finer grain size and greater surface area to volume ratio, it is expected to improve the ITZ moreSince silica fume
has metakaolin,
than a finer grain size and greater
however, in thissurface area to
study both volume
the ratio,
materials areit is expected
used to improve
to provide the ITZ
an insight more
into their
than metakaolin, however, in this study both the materials are used to provide an
relative performance. The cementitious mortars used are repair mortars, namely, Mix M and Mix P, asinsight into their
relative performance. The cementitious mortars used are repair mortars, namely, Mix M and Mix P,
described later in this section. Fibers are added to Mix M and a comparison is made to unmodified
as described later in this section. Fibers are added to Mix M and a comparison is made to unmodified
Mix M and Mix P.
Mix M and Mix P.
J. Compos. Sci. 2020, 4, 53 4 of 19

2.1.1. Polypropylene Fibers

In this study, a 100% virgin polypropylene microfiber was used. The mechanical properties of the
fiber as stated in the material safety data sheet [33] are listed in Table S1 available in the Supplementary
Materials section.

2.1.2. Repair Mortars

In this study, commercially available Mix M and Mix P were used which can be described as
cementitious mortar and polymer-modified cementitious mortar, respectively. For the preparation
of samples, only potable water was added to make the mix workable. As per the data sheets, Mix
M is especially suited for cold weather installations and the repair of freezer floors. It is available in
25 kg polyethylene-lined bags. Mix P is suited for vertical and overhead concrete repairs, including
precast/prestressed, tilt-up, post-tensioned, and cast-in-place concrete. It is available in bags of 22.7 kg.
The chemical composition of Mix M and Mix P are listed in Tables S2 and S3, respectively, available in
the Supplementary Materials section. The information was provided by the supplier.

2.1.3. Fiber Coating Materials

(a) Metakaolin: highly reactive class N pozzolan metakaolin was used in this study. Chemically, it
contained 100% calcined kaolin. The properties of the metakaolin used, as extracted from the safety
data sheet [34], are listed in Table S4 available in the Supplementary Materials section. (b) Silica fume:
properties of the silica fume used in this study are listed in Table S5 available in the Supplementary
Materials section as per the information from the material safety data sheet [35].

2.1.4. Adhesive
A multi-purpose adhesive with a compatible spray applicator is used. The adhesive is used to
assist the coating of fibers with metakaolin and silica fume. A spray adhesive ensures even distribution
and minimizes irregularities. Chemical composition extracted from the material safety data sheet [36]
are listed in Table S6 available in the Supplementary Materials section.

2.2. Mixture Proportioning

A total of six mixes were prepared including control samples, with and without fibers. The fibers
were coated with the help of an enclosed chamber. The chamber had a small opening fitted with a
nozzle. Through the opening, air was blown using an air compressor to keep fibers agitated. Using the
air compressor, the fibers were first dispersed inside the chamber, next the multi-purpose adhesive
was sprayed and the air compressor was used to coat the fibers as evenly as possible. Coated fibers
were obtained by dusting the SCM over the fibers coated with adhesive. The air compressor was used
again to distribute the SCM throughout the fibers inside the chamber. Figure 3 illustrates the basic
procedure. To separate the fibers from the adhered mesh-like formations, the fibers were chopped to
obtain filaments in the range of 3–6 mm length, thus maintaining an aspect ratio between 100 and 200.
It should be noted that this lab-based procedure does not guarantee complete coating of all fibers. The
unevenness of the coating might prove to be better in terms of binding with the mortar, however, this
aspect requires further detailed investigation. The SCM content was estimated to be about 19.96% by
weight as the percentage of the original untreated fibers taken for the coating procedure.
 J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 5 of 20
J. Compos. Sci. 2020, 4, 53 5 of 19
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 5 of 20

Figure 3. Chart showing the process of fiber preparation.

Figure 3. Chart showing the process of fiber preparation.

Thewater
watercontent
contentwas Figure
was used
used asas3.prescribed
Chart showing
prescribed in thetechnical
process ofsheet
fiber of
preparation.
The in the
the technical sheet ofthe
therepair
repairmixes
mixesused.
used.InInthethe
case where Mix M was used as the base material, the water content was slightly increasedfrom
case where Mix M was used as the base material, the water content was slightly increased fromthethe
Thetowater
prescribed takeintocontent
into wasthe
account usedwateras prescribed
adsorption in andthe technical sheet of theinrepair mixes used.toIn the
prescribed to take account the water adsorption and the
the expected
expectedreduction
reduction inworkability
workabilitydue due to
thecase where
PP fibers and Mixwas Mkept
wasconsistent
used as the base material,
throughout the including
the mixes, water contentcontrolwas slightly
mixes increased
without fibers. from
On the
the PP fibers and was kept consistent throughout the mixes, including control mixes without fibers.
prescribed
analysis of Mix toP,take
theinto account
amount the water
of fiber adsorption
was found and the
to be about 0.2%expected reduction
by weight. in workability
To simulate the samedue to
On analysis of Mix P, the amount of fiber was found to be about 0.2% by weight. To simulate the same
the PP fibersinand
reinforcement mixwas kept
M, the consistent
total amountthroughout
of the treated the mixes,
fiber wasincluding
also kept at control mixes
0.2% for without fibers. On
all specimens.
reinforcement in mix M, the total amount of the treated fiber was also kept at 0.2% for all specimens.
analysis of Mix
The various P, the
mixes amount
were of fiber
prepared was found
to capture to beofabout
the effect 0.2% by weight.
incrementally To simulate
adding layers the same
of coating
The various mixes were prepared to capture the effect of incrementally adding layers of coating
on reinforcement
the virgin fiber.in Themixfirst
M,mix
the contains uncoated
total amount virgin
of the PP fibers,
treated the next
fiber was mix contained
also kept at 0.2% for the
alladhesive
specimens.
on the virgin fiber. The first mix contains uncoated virgin PP fibers, the next mix contained the
layer only,
The the succeeding
various mix contained
mixes were prepared to metakaolin
capture the coated
effectover the adhesive,adding
of incrementally and thelayers
final of
mixcoating
adhesive layer only, the succeeding mix contained metakaolin coated over the adhesive, and the final
contained silica fiber.
on the virgin fumeThe coated overcontains
first mix the adhesive
uncoated (Figure
virgin4).PPAs discussed
fibers, the nextinmixearlier sections,
contained the
the adhesive
mix contained silica fume coated over the adhesive (Figure 4). As discussed in earlier sections, the
commercially
layer only,available repair mix
the succeeding mixP already
contained contains fibers. Hence,
metakaolin coatedno additional
over mixes were
the adhesive, andprepared
the final mix
commercially available repair mix P already contains fibers. Hence, no additional mixes were prepared
with mix P. Instead,
contained silica the
fume mixcoated
was usedover as is to adhesive
the serve as a comparative
(Figure 4). As mixdiscussed
to this study.in Table
earlier1 lists the the
sections,
with mix P. Instead,
mixcommercially
designs and the the mix was
number of used as cast
samples is tofor
serve
each asmix.
a comparative mix to this study. Table 1 lists the
available repair mix P already contains fibers. Hence, no additional mixes were prepared
mix designs and the number of samples cast for each mix.
with mix P. Instead, the mix was used as is to serve as a comparative mix to this study. Table 1 lists the
mix designs and the number of samples cast for each mix.

Figure4.
Figure 4. Different
Different mix
mix designs
designs with
with Mix
Mix M
Mas
asthe
thebase
basematerial.
material.

Table 1. Different mix designs and the number of samples cast.

Figure 4. Different mix designs with Mix M as the base material.

Table 1. Different mix designs and the number of samples cast.

 J. Compos. Sci. 2020, 4, 53 6 of 19

Table 1. Different mix designs and the number of samples cast.

SI Water Content (% Working Number of Samples Cast

Mixture Mix ID by Weight of the Time Fiber Type
No Cubes Coupons 6 ofBeams
Repair Mortar)
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW (mins) 20
Mix P Commercial
1 (commercial mix PF Water17
Content 5 fiber-reinforced 6 6 of Samples6Cast
Number
with fibers) Working repair mortar
SI (% by Weight of
Mixture
Mix M (control Mix ID Time Fiber Type
No the Repair Cubes Coupons Beams
2 mix M without MC 10 45
(mins) No fiber added 6 6 6
fibers) Mortar)
Mix P (commercial mix Commercial fiber-
Micropolypropylene
1 Mix M with PF 17 5 6 6 6
3 with fibers) MFU 10 45 reinforced
fibers withrepair
no mortar 6 6 6
untreated fibers
Mix M (control mix M coating
2 MC 10 45 No fiber added 6 6 6
Mixfibers)
without M with Micropolypropylene
4 Mix Madhesive-coated
with untreated
MFA 10 45 fibers coated with
Micropolypropylene
6 6 6
3 fibers MFU 10 45 spray adhesive only 6 6 6
fibers fibers with no coating
Micropolypropylene
Micropolypropylene
Mix adhesive-
Mix M with M with fibers coated with
4 5 metakaolin-coated MFA
MFM 10
10 45
45 fibersadhesive
spray coated with
andspray 6 6 6 6 6 6
coated fibers
fibers dusted withonly
adhesive
metakaolin
Micropolypropylene
Mix M with Micropolypropylene
5
Mixmetakaolin-
M with MFM 10 45
fibers coated with spray
6 6 6
fibers coated with
coated silica
fibers adhesive and dusted
6 MFS 10 45 spray adhesive and 6 6 8
fume-coated with metakaolin
dusted with
fibers
silica fume
Micropolypropylene
Mix M with silica fume- fibers coated with spray
6 MFS 10 45 6 6 8
coated fibers adhesive and dusted
2.3. Specimen Preparation
with silica fume
Mortar cubes were cast in accordance with ASTM C109 [37]. Each of the cubes (50 mm in size) was
cast in2.3.
two Specimen
layers Preparation
with a hand tamping technique used for consolidation. A total of 6 cubes for each
mix were cast forcubes
Mortar determination
were cast inofaccordance
compressive withstrength.
ASTM C109 Briquette
[37]. Eachsamples prepared
of the cubes (50 mm were cast and
in size)
tested was cast in twothe
to determine layers withstrength
tensile a hand tamping technique
of the mixes. Theused for consolidation.
briquettes A total of 6 of
had a cross-section cubes for mm2
645.16
at the each
neck.mix were castmolds
Briquette for determination
used wereofincompressive
accordance strength. Briquette
with ASTM samples
C307 [38].prepared
Both thewere widthcastof the
and tested to determine the tensile strength of the mixes. The briquettes had
neck and thickness was 25.4 mm as per the provisions of ASTM. A total of 6 specimens for each mix a cross-section of 645.16
mm2 at the neck. Briquette molds used were in accordance with ASTM C307 [38]. Both the width of
were prepared to test the tensile strength. In addition to the ASTM standard tests on mortars as stated
the neck and thickness was 25.4 mm as per the provisions of ASTM. A total of 6 specimens for each
above,mix
beams of size (30 mm × 30 mm × 100 mm) were cast. Figure 5 shows the cast specimens of
were prepared to test the tensile strength. In addition to the ASTM standard tests on mortars as
each type.
stated above,specimens
These beams of size were
(30 mmprepared
× 30 mm to×determine
100 mm) were thecast.
modulus
Figure 5ofshows
rupture in flexure
the cast specimens for each
of the of
mixes. A total
each type. Theseofspecimens
6 beams were wereprepared
prepared for each mixture
to determine the modulustype. Immediately
of rupture in flexureafter molding,
for each
specimens
of thewere
mixes.sealed
A totalinofplastic
6 beams sheets
were to minimize
prepared the evaporation
for each mixture type. of moisture from
Immediately the fresh mix.
after molding,
specimens
Specimens werewere sealed
stored at 23 ± 2 ◦ Csheets
in plastic for 24to h
minimize the evaporation
before demolding. of moisturesamples
Demolded from the were
fresh mix.
stored in
Specimens were stored at 23 ◦ ± 2 °C for 24 h before demolding. Demolded
water at a temperature of 23 ± 2 C. All the mixes were immersed in separate water containers samples were stored toin avoid
water at a temperature of 23 ± 2 °C. All the mixes were immersed in separate water containers to
cross-contamination from the effect of leaching of free lime or constituents of SCMs.
avoid cross-contamination from the effect of leaching of free lime or constituents of SCMs.

(a) (b) (c)

5. Specimens
FigureFigure castcast
5. Specimens forfor
testing:
testing:(a)
(a)mortar cube,(b)
mortar cube, (b)beam,
beam, and
and (c) (c) dog-bone/coupon.
dog-bone/coupon.
J. Compos. Sci. 2020, 4, 53 7 of 19

2.4. Experimental Investigation

J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 7 of 20
2.4.1. Compressive Strength Test
2.4. Experimental Investigation
Sides of the mortar cubes were evened out using sandpaper to ensure even load distribution from
the testing machine to the specimen face. Specimens were taken out of the curing water and allowed
2.4.1. Compressive Strength Test
to attain saturated surface dry condition before carrying out tests. Tests were performed in accordance
Sides of the mortar cubes were evened out using sandpaper to ensure even load distribution
with ASTM C109 [37]. FORNEY compression testing machine F-650 was used in conjunction with
from the testing machine to the specimen face. Specimens were taken out of the curing water and
FORNEY TestPilot digital indicator for this test. The machine has a load capacity of 2891 kN. The load
allowed to attain saturated surface dry condition before carrying out tests. Tests were performed in
was applied at a rate of 0.6 MPa/s. Tests were conducted at 14 and 28 days, and three specimens were
accordance with ASTM C109 [37]. FORNEY compression testing machine F-650 was used in
tested at each
conjunctionage.
with FORNEY TestPilot digital indicator for this test. The machine has a load capacity of
2891 kN. The load was applied at a rate of 0.6 MPa/s. Tests were conducted at 14 and 28 days, and
2.4.2.three
Tensile Strength
specimens Test
were tested at each age.
Specimens were taken out of the curing tank and allowed to attain saturated surface dry condition
2.4.2. Tensile Strength Test
before carrying out tests. A total of at least 6 specimens per mix were molded. The test was conducted
using PASCO ® Materials
Specimens were taken out Machine
Testing of the curing tank and
ME-8236 usedallowed to attain with
in conjunction saturated surface
briquette dry The
grips.
condition before carrying out tests. A total of at least 6 specimens per mix were molded.
machine had a load cell capacity of 7100 N. In its original capacity, ME-8236 operates using a manual The test was
conducted using PASCO ® Materials Testing Machine ME-8236 used in conjunction with briquette
crankshaft, to regulate the process of controlling speed and load rate. The machine was modified by
grips. The machine had a load cell capacity of 7100 N. In its original capacity, ME-8236 operates using
adding an electric motor BMUD60-A2 from Oriental Motor® . The setup is shown in Figure 6 below.
a manual crankshaft, to regulate the process of controlling speed and load rate. The machine was
The motor comprises a brushless DC Motor Driver compatible with a single-phase 100–120 VAC power
modified by adding an electric motor BMUD60-A2 from Oriental Motor ® . The setup is shown in
supply. Using the motor,
Figure 6 below. The motor thecomprises
speed was set to 50DC
a brushless rpm, which
Motor translated
Driver to with
compatible a displacement
a single-phaserate of
0.5 mm/min
100–120 onVAC thepower
briquette sample.
supply. UsingThis
the automation
motor, the speedin thewas
machine resulted
set to 50 in a much
rpm, which moreto
translated constant
a
loading rate. Therate
displacement machine was coupled
of 0.5 mm/min on thewith
briquette sample.®This
the PASCO 550automation
Universal inInterface to connect
the machine resultedto the
PASCOin a Capstone
much moresoftware.
constant loading rate. The of
The deflection machine was coupled
the coupon sampleswith thedetermined
was PASCO ® 550 byUniversal
the software
Interface to connect to the PASCO Capstone software. The deflection of
from the number of rotations made by the threads of the machine. The deflection and loads the coupon samples was were
recorded at a sampling frequency of 25 Hz. The direct tensile test was carried out at 14 and 28The
determined by the software from the number of rotations made by the threads of the machine. days of
deflection and loads were recorded at a sampling frequency of 25 Hz. The direct tensile test was
curing and six specimens were tested for each age.
carried out at 14 and 28 days of curing and six specimens were tested for each age.

Figure 6. Details of the direct tensile strength test in progress.

Figure 6. Details of the direct tensile strength test in progress.
J. Compos. Sci. 2020, 4, 53 8 of 19

J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 8 of 20

2.4.3. Three-Point Flexural Test

2.4.3. Three-Point Flexural Test
Mortar beams were cast to determine the flexural strength (modulus of rupture). To carry out
Mortar beams were cast to determine the flexural strength (modulus of rupture). To carry out
flexural strength tests using the three-point bending setup, the same PASCO® ME-8236 equipment
flexural strength tests using the three-point bending setup, the same PASCO ® ME-8236 equipment
as described above was used. The briquette grips were replaced by the ME-8237 materials bending
as described above was used. The briquette grips were replaced by the ME-8237 materials bending
accessory provided by PASCO® . The accessory included a plunger and adjustable support anvils. For
accessory provided by PASCO ® . The accessory included a plunger and adjustable support anvils.
this study, the span length between the anvils was kept constant at 88 mm (Figure 7). Displacement
For this study, the span length between the anvils was kept constant at 88 mm (Figure 7).
measurements were recorded with the help of the LD620-25 linear variable differential transformer
Displacement measurements were recorded with the help of the LD620-25 linear variable differential
(LVDT) produced by OMEGA® . The LVDT had a range of 25 mm with an excitation voltage of
transformer (LVDT) produced by OMEGA® . The LVDT had a range of 25 mm with an excitation
10–30 Vdc @ 25 mA and had an output of ± 5 Vdc with a bandwidth of 500 Hz. The LVDT was
voltage of 10–30 Vdc @ 25 mA and had an output of ± 5 Vdc with a bandwidth of 500 Hz. The LVDT
kept in contact at the midspan of the beam with the help of stainless-steel L-brackets attached to the
was kept in contact at the midspan of the beam with the help of stainless-steel L-brackets attached to
beams using fast-setting epoxy resin (Figure 8). A total of at least 6 specimens per mix were cast.
the beams using fast-setting epoxy resin (Figure 8). A total of at least 6 specimens per mix were cast.
Three-point bending tests were conducted at a strain rate of 0.5 mm/min at 14 and 28 days of curing.
Three-point bending tests were conducted at a strain rate of 0.5 mm/min at 14 and 28 days of curing.
Three specimens were tested at each testing age.
Three specimens were tested at each testing age.

Figure 7.
Figure 7. Details
Details of
of the
the flexure
flexure strength
strength test
test in
in progress.
progress.

2.4.4. Microscopic Analysis

The ESTF were observed under an optical microscope for a preliminary examination of the
metakaolin and silica fume coatings. Trinocular stereo zoom microscope produced by AmScope ©
was used for the examination. Specifications of the microscope include 7–45× continuous zoom
magnification power with a super widefield optical system and a 10 cm working distance. It is
also enabled with a trinocular port that added photo-capturing capability once interfaced with a
computer system.
J. Compos. Sci. 2020, 4, 53 9 of 19
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 9 of 20

Figure8.8.Arrangement
Figure Arrangementof
ofthe
thedisplacement
displacementmeasuring
measuringset
setup
upfor
forbeams.
beams.

2.4.4.Specimens
Microscopic Analysiscoated fiber samples (MFM and MFS) were analyzed under a SEM to check
containing
for the coating
The ESTFofwerefibersobserved
and bonding
underwithan the matrix.
optical Elemental
microscope formapping on eachexamination
a preliminary fiber sampleofwas the
done on fiber surfaces to evaluate the effectiveness of the coating method
metakaolin and silica fume coatings. Trinocular stereo zoom microscope produced by AmScope © was used. Additionally, the
interface
used forbetween fiber and matrix
the examination. was analyzed
Specifications of tothe
evaluate the effect
microscope on the interfacial
include transition zone.
7–45× continuous zoom
Scanning electron
magnification microscopy
power was done
with a super using optical
widefield Hitachisystem
S-4800 FESEM
and a 10(Figure S1 in the
cm working Supplementary
distance. It is also
Materials
enabled with section). The equipment
a trinocular has a 1photo-capturing
port that added and 1.4 nm resolution
capabilityat 15 andinterfaced
once 1 kV, respectively, and a
with a computer
magnification
system. range from 30× to 800,000×. Slices from dog-bone samples were cut using a wet tile
saw. The cut slices were kept
Specimens containing in anfiber
coated airtight chamber
samples (MFM attached
and MFS) to were
a vacuum pump
analyzed immediately
under after
a SEM to check
the cutting process was over. This was done for a period of at least 3 days
for the coating of fibers and bonding with the matrix. Elemental mapping on each fiber sample wasto retard the formation
of any on
done hydration product
fiber surfaces toafter the samples
evaluate are cut. The
the effectiveness of samples
the coating were placedused.
method in a vacuum chamber
Additionally, the
immediately
interface between fiber and matrix was analyzed to evaluate the effect on the interfacial transition were
after being cut and surface dried for a period of at least 3 days. The sliced samples zone.
further
Scanning cleaned andmicroscopy
electron vacuumed for wasadone
period of 24Hitachi
using h usingS-4800
the Hitachi
FESEM ZoneSEM
(Figure S1desktop
in the sample cleaner,
Supplementary
which usessection).
Materials UV light Theto equipment
remove contaminants.
has a 1 and 1.4Thenm Cressington
resolution 208C
at 15 was
and 1used
kV, to carbon coatand
respectively, thea
samples to allow SEM imaging on the nonconductive samples. Carbon coating
magnification range from 30× to 800,000×. Slices from dog-bone samples were cut using a wet tile saw. of samples is also
recommended
The cut slices by werethekept
manufacturer in cases
in an airtight where
chamber EDX is to
attached to be done as pump
a vacuum carbonimmediately
does not absorbafterand
the
fluoresce as much as other coatings.
cutting process was over. This was done for a period of at least 3 days to retard the formation of any
hydration product after the samples are cut. The samples were placed in a vacuum chamber
3. Results and Discussion
immediately after being cut and surface dried for a period of at least 3 days. The sliced samples were
further
3.1. cleaned
Strength and vacuumed for a period of 24 h using the Hitachi ZoneSEM desktop sample cleaner,
in Compression
which uses UV light to remove contaminants. The Cressington 208C was used to carbon coat the
Figure 9 shows the results of the compressive tests done for all the mixes measured at both 14-
samples to allow SEM imaging on the nonconductive samples. Carbon coating of samples is also
and 28-day strength. Average compressive strength is presented for various mixes with error bars.
recommended by the manufacturer in cases where EDX is to be done as carbon does not absorb and
fluoresce as much as other coatings.

3. Results and Discussions

J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 10 of 20

3.1. Strength in Compression

J. Compos.
Figure Sci. 2020, 4,the
9 shows 53
results of the compressive tests done for all the mixes measured at both 14- 10 of 19
and 28-day strength. Average compressive strength is presented for various mixes with error bars.

Compressive strength
80
Compressive Strength (MPa)

70
60
50
40
30 60.51 62.13 63.49
54.87 54.06 57.79
47.64 51 49.52
44.28 46.51
20
33.68
10
0
PF MC MFU MFA MFM MFS
Mix Design

14 day strength 28 day strength

Figure 9. Compressive
Figure Strength
9. Compressive of different
Strength mixesmixes
of different at 14 and
at 1428and
days.
28 days.

Compared
Compared to the basebase
to the material (MC),
material the mix
(MC), the reinforced with with
mix reinforced untreated polypropylene
untreated fiber fiber
polypropylene
(MFU) showed a drop in compressive strength by 2.43% at 14-day age and 9.32%
(MFU) showed a drop in compressive strength by 2.43% at 14-day age and 9.32% at 28-day age. When at 28-day age. When
studying
studying the the
effect of treatment
effect of treatmentof fibers,
of fibers,metakaolin-treated
metakaolin-treatedfibersfibers
(MFM) showed
(MFM) an increase
showed of
an increase of
7.05% (14-day
7.05% strength)
(14-day strength)and and
15.71% (28-day
15.71% (28-daystrength) on average,
strength) whereas
on average, silica silica
whereas fume-coated fibers fibers
fume-coated
(MFS)
(MFS)showed
showed ananimprovement
improvementof of 3.94% (14-day strength)
3.94% (14-day strength)and and5.32%
5.32% (28-day
(28-day strength)
strength) fromfromuntreated
untreated polypropylene fibers (MFU) in the same matrix. On comparing
polypropylene fibers (MFU) in the same matrix. On comparing the base material (MC) the base material (MC) withwith the
the commercially
commercially available
available fiber-reinforced
fiber-reinforced repair
repair material, the increase in strength was 38.09% at14
material, the increase in strength was 38.09% at 14 days
days and 36.65% at
and 36.65% at 28 days.28 days.
TheThe
compressive
compressive strength due due
strength to metakaolin
to metakaolin increased by 13.47%
increased whenwhen
by 13.47% comparing 14-day14-day
comparing MFU MFU
andandMFM MFM samples.
samples. Other studies
Other [39] showed
studies [39] showed an increase of 3.27%
an increase on replacing
of 3.27% 5% cement
on replacing with with
5% cement
metakaolin. In this study, by using a much lower amount of metakaolin, the strength increased by
metakaolin. In this study, by using a much lower amount of metakaolin, the strength increased by
13.47% as compared to 3.27%.
13.47% as compared to 3.27%.
On comparing the 28 days cured samples, the cube strength of MFM increased by 15.71%
On comparing the 28 days cured samples, the cube strength of MFM increased by 15.71% compared
compared with MFU. A study [26] showed an increase of as high as 16.8% in compressive strength
with MFU. A study [26] showed an increase of as high as 16.8% in compressive strength on the addition
on the addition of 20% metakaolin which is 100 times the amount of metakaolin used in the present
of 20% metakaolin which is 100 times the amount of metakaolin used in the present study. The same
study. The same study [26] also showed an increase of 7.9% in compressive strength in the case of
study [26] also showed an increase of 7.9% in compressive strength in the case of silica fume, whereas
silica fume, whereas the present study used 0.01 times the amount of silica fume to report a cube
the present study used 0.01 times the amount of silica fume to report a cube strength improvement of
strength improvement of 5.32%. This further suggests that the position of the SCM in addition to the
SCM 5.32%. This further
properties suggests
itself plays that the position
an important role in the of mechanical
the SCM in strength
addition ofto the
the material.
SCM properties itself plays
Researchers
an important role in the mechanical strength of the material. Researchers
[40] have shown interest in metakaolin due to its microfiller and pozzolanic properties. Pozzolanic [40] have shown interest in
metakaolin
materials suchdue as to its microfiller
metakaolin andand pozzolanic
silica fume react properties. Pozzolanic to
with portlandite materials
produce such as metakaolin
additional
and silica fume react with portlandite to produce additional cementitious
cementitious gel [41]. In the case of metakaolin, the pozzolanic property is the ability to react gel [41]. In the
withcase of
metakaolin, the pozzolanic property is the ability to react with calcium
calcium hydroxide in the presence of water to form hydrated silicate gel products that possess hydroxide in the presence of
water to form
cementitious hydrated
properties silicate
[42,43]. gel products
Although that possessfor
the calculations cementitious properties
the improvements [42,43].
were madeAlthough
using the
the averages, it is essential to keep in mind that these averages were found out within the limitsmind
calculations for the improvements were made using the averages, it is essential to keep in of that
these averages were found out within the limits of experimental error
experimental error which have been quantified in terms of the standard deviation (as included in which have been quantified in
terms
Figure 9). of the standard deviation (as included in Figure 9).
Further, a statistical validation test was performed on the compressive strength results using the
one-way analysis of variance (ANOVA) technique in MATLAB. The one-way ANOVA was conducted to
compare the effect of coating on the compressive strength. The ANOVA technique has been previously
used by researchers [44] to understand the statistical variation in tests done on mortars. The statistical
 J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 11 of 20

Further, a statistical validation test was performed on the compressive strength results using the
J. Compos. Sci. 2020, 4, 53 11 of 19
one-way analysis of variance (ANOVA) technique in MATLAB. The one-way ANOVA was
conducted to compare the effect of coating on the compressive strength. The ANOVA technique has
been previously
confidence usedofby
of the effect theresearchers
coating on [44] to understand
the compressive the statistical
strength variation
was analyzed. Theinprobability
tests donep that
on
mortars. The statistical confidence of the effect of the coating on the compressive
the null hypothesis is true was determined for the three critical mixes, namely, MFU, MFM, and MFS. strength was
Aanalyzed.
thresholdTheof pprobability
= 0.05 wasp considered
that the null and
hypothesis is true was were
the comparisons determined
made.for thep three
The critical
values mixes,
greater than
namely, MFU, MFM, and MFS. A threshold of p = 0.05 was considered and the comparisons
the threshold value of 0.05 were considered statistically insignificant. On comparing the three mixes, were
made.
the valueThe
forppvalues
for 14greater
days wasthan the threshold
found valueThe
to be 0.0033. of 0.05 were considered
analysis of variancestatistically
showed that insignificant.
the effect of
On comparing the three mixes, the value for p for 14 days was found to be 0.0033. The analysis of
the coating on the compressive strength was significant, p = 0.0033 for 14-day strength. Similarly, the
variance showed that the effect of the coating on the compressive strength was significant, p = 0.0033
28-day strength was also validated using the one-way ANOVA test, p = 0.0295. Since the probability p
for 14-day strength. Similarly, the 28-day strength was also validated using the one-way ANOVA
was less than the threshold in both the cases, this shows that the comparisons are significant and the
test, p = 0.0295. Since the probability p was less than the threshold in both the cases, this shows that
coating does improve the compressive strength.
the comparisons are significant and the coating does improve the compressive strength.
3.2. Strength in Direct Tension
3.2. Strength in Direct Tension
Figure 10 shows the results of the direct tension tests conducted on mortar briquettes (also referred
Figure 10 shows the results of the direct tension tests conducted on mortar briquettes (also
to as dog-bones or coupons) for all the mixes measured at both 14- and 28-day strength. Average
referred to as dog-bones or coupons) for all the mixes measured at both 14- and 28-day strength.
tensile strength is presented for various mixes with error bars.
Average tensile strength is presented for various mixes with error bars.

Tensile strength
4
3.5
Tensile Strength (MPa)

3
2.5
2
3.39
1.5 2.99 2.92 3.14
2.75 2.75 2.88 2.81
2.48 2.7 2.5
1 1.85
0.5
0
PF MC MFU MFA MFM MFS
Mix Design

14 day strength 28 day strength

Figure 10. Tensile strength of different mixes with 14 and 28 days strength.
Figure 10. Tensile strength of different mixes with 14 and 28 days strength.

Thetensile
The tensilestrength
strengthwas
wascalculated
calculatedbyby dividing
dividing the
the peak
peak (maximum)
(maximum)load loadby bythe
thecross-sectional
cross-sectional
area of the failure plane which was calculated by determining the actual length
area of the failure plane which was calculated by determining the actual length and depth and depth
at the at the
section
ofsection
failureofoffailure of the dog-bone
the dog-bone specimens
specimens using using
digitaldigital calipers.
calipers. The The following
following is the
is the equation
equation usedto
used
to calculate the tensile strength of the
calculate the tensile strength of the mixes: mixes:

𝑃
𝑇𝑒𝑛𝑠𝑖𝑙𝑒 𝑆𝑡𝑟𝑒𝑛𝑔𝑡ℎ (𝑀𝑃𝑎) =P (1)
Tensile Strength (MPa) = 𝑏×𝑑 (1)
b×d
where P is peak load in N, b is the width, and d is the depth of the coupon at failure surface in
where P is peak load in N, b is the width, and d is the depth of the coupon at failure surface in millimeters.
millimeters.
Given
Giventhe therelatively high
relatively highstandard
standard deviations
deviations inin
thethefirst peak
first peakvalues, thethe
values, tensile strength
tensile strengthdoes not
does
not show
show any significant
any significant difference
difference in the in the addition
addition of to
of fibers fibers to the
the base base material
material (MC). PF (MC). PF mixture
mixture showed
showed
the highestthe highest strengths
strengths both at 14both
and at
2814 andof28curing.
days days ofThecuring. The relatively
relatively high strength
high strength in mix PFin possibly
mix PF
possiblya indicates
indicates a better
better overall mixoverall
designmix design
of the of the
product. product. Additionally,
Additionally, it also
it also possibly possibly
indicates theindicates
presence
ofthe
an presence
inclusiveof an compatible
and inclusive and compatible
mix of fibers bymixthe
of supplier.
fibers by the For supplier. For further investigation,
further investigation, fibers in mix
P (PF mix) were studied under SEM and an optical microscope. This revealed a better dispersion of
 J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 12 of 20
J. Compos. Sci. 2020, 4, 53 12 of 19
fibers in mix P (PF mix) were studied under SEM and an optical microscope. This revealed a better
dispersion of fibers in the commercial mix P. The diameter of fibers in the commercial mix P (PF) was
fibers in the commercial
found to be aboutmix15 µ P. The diameter
, whereas the fibersofused
fibers
andin the commercial
modified mix
in this study for Pother
(PF)mixes
was were
found of to be
about 15 µ,30whereas
µ in diameter.
the fibers used and modified in this study for other mixes were of 30 µ in diameter.
The area under the tensile curve (Figure 11) represents the toughness of the specimens.
The area under the tensile curve (Figure 11) represents the toughness of the specimens. Toughness
Toughness of MFU, MFM, and MFS samples was 766.06, 790.03, and 829.40 N-mm, respectively.
of MFU, MFM, and MFS samples was 766.06, 790.03, and 829.40 N-mm, respectively. Samples reinforced
Samples reinforced with treated fiber (including MFM and MFS) showed ductile behavior, and the
with treated fiber (including
toughness MFM
value is slightly andthan
higher MFS) thatshowed ductile
of untreated fibersbehavior, and the
coupons (MFU). toughness
Albeit, value
this is not a is
slightly higher than improvement
significant that of untreated fibers
and may notcoupons (MFU). Albeit,
be representative this
of all the is not aThis
samples. significant improvement
aspect needs to be
and may notstudied in future studies.of all the samples. This aspect needs to be studied in future studies.
be representative

Figure 11.Figure 11. vs.

Load Load displacement
vs. displacement curvescomparing
curves comparing untreated
untreated polypropylene
polypropylenefiberfiber
(MFU),
(MFU),
metakaolin-treated fibers (MFM), and silica fume-coated fibers (MFS).
metakaolin-treated fibers (MFM), and silica fume-coated fibers (MFS).
Fiber-reinforced samples using laboratory prepared fibers (MFU, MFA, MFM, and MFS)
Fiber-reinforced samples using laboratory prepared fibers (MFU, MFA, MFM, and MFS) exhibited
exhibited ductile fracture after reaching peak loads. The fracture planes resembled ductile fracture
ductile fracture
patternsafter reaching
observed peak
in metals loads.toThe
subjected fracture
uniaxial planes
tension. resembled
This is ductile fracture
a possible indicator of the shiftpatterns
to
observed plastic
in metals subjected to uniaxial tension. This is a possible indicator of the shift to12).
failure on adding fibers as opposed to brittle failure in unreinforced samples (MC) (Figure plastic
failure on These
adding fibers
results astypical
were opposed to brittle
for most of the failure in unreinforced
fiber-reinforced samples
samples tested under(MC)
direct(Figure
tension. 12). These
results were typical for most
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW
of the fiber-reinforced samples tested under direct tension. 13 of 20

Figure 12. 12.

Figure Brittle failure
Brittle of unreinforced
failure mortar
of unreinforced mix,
mortar base
mix, material
base (MC)
material (left)
(MC) andand
(left) ductile cupcup
ductile andand
cone fracture
cone for for
fracture reinforced mortar,
reinforced MFS
mortar, (right).
MFS (right).

3.3. Flexural Strength

Figure 13 shows a schematic diagram of the three-point bending test. The modulus of rupture
was calculated using the following formula:
J. Compos. Sci. 2020, 4, 53 13 of 19

Figure
3.3. Flexural 12. Brittle failure of unreinforced mortar mix, base material (MC) (left) and ductile cup and
Strength
cone fracture for reinforced mortar, MFS (right).
Figure 13 shows a schematic diagram of the three-point bending test. The modulus of rupture
3.3. Flexuralusing
was calculated Strength
the following formula:
Figure 13 shows a schematic diagram of the three-point bending test. The modulus of rupture
was calculated using the following formula: 3PS
σmax = (2)
2bd2
3𝑃𝑆
where σmax = modulus of rupture in MPa, P𝜎=𝑚𝑎𝑥 peak=load
(2)
2𝑏𝑑 2applied on the beam in N, S = support span in
mm (kept
whereconstant at 88 mm
𝜎𝑚𝑎𝑥 = modulus for the in
of rupture MPa, Pb==peak
study), width
loadofapplied
the beam ( 30
on the mm),
beam and
in N, = depth
S =dsupport of the beam
span
(30 mm).
in mm (kept constant at 88 mm for the study), b = width of the beam ( 30 mm), and d = depth of the
beam (30 mm).

Figure 13. Schematic diagram of three-point bending test on mortar beam specimen.
Figure 13. Schematic diagram of three-point bending test on mortar beam specimen.
Figure 14 shows the flexural strength results of the mortar beams for all the mixes measured at
Figure
both 14-14 shows
and the
28-day flexural
strength. strength
Average results
flexural of the
strength is mortar beams
presented for allmixes
for various the mixes measured at
with error
both 14-
bars.and 28-day strength. Average flexural strength is presented for various mixes with error bars.
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 14 of 20

Flexural strength
9
Flexural Strength (MPa)

8
7
6
5
4 8.01
6.59 6.71 7.22 6.61 6.75 6.99 6.99 6.55 6.48 6.8
3 5.78
2
1
0
PF MC MFU MFA MFM MFS
Mix Design

14 day strength 28 day strength

Figure14.
Figure 14.Flexural
Flexural strength
strength of
of different
different mixes
mixes with
with 14-
14- and
and 28-days
28-daysstrength.
strength.

Considering the first peak behavior, the results do not indicate any significant change in the
modulus of rupture after the addition of fibers. This might be a consequence of the low dosage of
fibers (0.2% by binder weight), which, in turn, means that the surface area of fiber coated with the
SCM is small. Other researchers [45] reported an improvement of as small as 1.94% when 5%
metakaolin was replaced in OPC. This indicates that the addition of small amounts of metakaolin
J. Compos. Sci. 2020, 4, 53 14 of 19

Considering the first peak behavior, the results do not indicate any significant change in the
modulus of rupture after the addition of fibers. This might be a consequence of the low dosage of
fibers (0.2% by binder weight), which, in turn, means that the surface area of fiber coated with the SCM
is small. Other researchers [45] reported an improvement of as small as 1.94% when 5% metakaolin
was replaced in OPC. This indicates that the addition of small amounts of metakaolin does not have a
significant impact on the bending strength of concrete.
One possible reason for the relatively neutral response of the flexural strength to the coating
could be the poor workability. On addition of polypropylene fibers, the workability of cementitious
composites reduces with an increase in the dosage of fibers [46,47]. The reduced workability is a likely
factor that prevented proper compaction and placement of the mix in the small beam molds. This
might have led to the reduced strength when coated fibers were used in the mix.

3.4. Optical Microscopy

Figure 15 shows a preliminary investigation on the coated fiber samples using optical microscopy.
A scale bar is also included in the images. Figure 15a shows virgin untreated polypropylene fibers
without any coating, Figure 15b shows polypropylene fibers treated with metakaolin coating, and
Figure 15c shows silica fume-coated polypropylene samples. Visually in Figure 15b,c, it appears that
the fiber is uniformly coated either heavily or lightly with the SCM. Even distribution and uniformity
of pozzolan material is further investigated under an SEM in Section 3.5.

J. Compos. Sci. 2020, 4, x FOR PEER REVIEW 15 of 20

(a) (b)

(c)

Figure 15. Images showing various fibers used in the study: (a) untreated polypropylene (10×
Figure 15. Images showing various fibers used in the study: (a) untreated polypropylene (10×
magnification) fiber, (b) polypropylene fiber coated with metakaolin (45× magnification), and (c) silica
magnification) fiber, (b) polypropylene fiber coated with metakaolin (45× magnification), and (c) silica
fume coatedfume
polypropylene fiber (45×
coated polypropylene magnification).
fiber (45× magnification).

3.5. Scanning
3.5.Electron
Scanning Microscopy
Electron Microscopy
After the
After the SCM SCM coating
coating procedure
procedure waswas carriedout
carried out on
on fibers,
fibers,they were
they analyzed
were under an
analyzed SEM an SEM
under
and energy dispersive X-ray spectroscopy (EDS). The microscopy images revealed the presence of a
and energy dispersive X-ray spectroscopy (EDS). The microscopy images revealed the presence of a
varying concentration of SCM on the fiber surface. However, pozzolanic materials seem to be present
varying concentration
throughout theofsurface.
SCM on the
Since thefiber
effectsurface. However,and
of ITZ is progressive pozzolanic materials
is most significant in theseem to be present
first 15–20
µ m closest to the reinforcement [6], even a small amount of coating can be sufficient to provide the
desired results. The evenness of the coating was not visible using optical microscopy owing to the
fine nature of the particles of the SCMs used; however, it was evident under the SEM. Figure 16a
distinctly shows the coating of metakaolin as brighter spots on the surface of the fiber. Bruker
Quantax (EDS) System was used for X-ray spectroscopy to reveal the elements in the sample.
The spectroscopy revealed peaks corresponding to elements such as silicon, oxygen, and calcium.
J. Compos. Sci. 2020, 4, 53 15 of 19

throughout the surface. Since the effect of ITZ is progressive and is most significant in the first 15–20 µm
closest to the reinforcement [6], even a small amount of coating can be sufficient to provide the desired
results. The evenness of the coating was not visible using optical microscopy owing to the fine nature
of the particles of the SCMs used; however, it was evident under the SEM. Figure 16a distinctly shows
the coating of metakaolin as brighter spots on the surface of the fiber. Bruker Quantax (EDS) System
was used for X-ray spectroscopy to reveal the elements in the sample. The spectroscopy revealed
peaks corresponding to elements such as silicon, oxygen, and calcium. The equipment demonstrates
the ability to show the true spatial distribution of each element of interest in the given sample. The
magnification level was set at 200× with an accelerating voltage of 15 kV and a working distance of
17.4 mm for the parent image. Using Figure 16a as the parent image, elemental mapping was done on
it to reveal the positioning of the elements which showed spectrum peaks (Figure 16b). The elemental
mapping revealed the positioning of silicon (shown in Figure 16d) and oxygen (shown in Figure 16e)
from the pozzolan (metakaolin) on the fiber surface. As indicated by the datasheet of metakaolin
and other studies [48], it was inferred that the primary components in metakaolin were oxides of
aluminum and silicon. Elements such as silicon and oxygen, which corresponded to the peaks in
Figure 16b, are seen with their spatial distribution in Figure 16d,e. Figure 16d,e shows the16distribution
J. Compos. Sci. 2020, 4, x FOR PEER REVIEW of 20
of the constituents of the SCM. Outline of the fibers in the parent image can be made out in the images
showing image can be made
elemental mapping, out in indicating
the images showing elemental
the presence mapping,
of SCM indicating
on the surfacethe
ofpresence of SCM
the fiber.
on the surface of the fiber.

(a) (b)

(c) (d)

Figure 16. Cont.

J. Compos. Sci. 2020, 4, 53 16 of 19

(c) (d)

(e)

Figure
Figure 16. SEM 16.images
SEM images of metakaolin-coated
of metakaolin-coated fibers
fibers (clockwise
(clockwise from
from topleft):
top left):(a)
(a)image
imageshowing
showing coating
coating at 200× magnification, (b) spectrum showing the constituent peaks, (c) elemental map of
at 200× magnification, (b) spectrum showing the constituent peaks, (c) elemental map of oxygen and
oxygen and silicon, (d) elemental map of silicon only, and (e) elemental map showing oxygen only.
silicon, (d) elemental map of silicon only, and (e) elemental map showing oxygen only.

4. Conclusions and Recommendations

Based on the study conducted, the following conclusions are drawn:

• The compressive strength improved on addition of metakaolin-coated fibers when comparing

MFU and MFM samples. In this study, by using 1/25th of the amount of metakaolin used in other
studies, the strength increased by 13.47% as compared to the reported 3.27%.
• The compressive strength of a cementitious composite is affected by not only the amount of SCM
but also by the position they occupy in the matrix. By concentrating the SCM on the parts of the
matrix where it is needed the most (boundaries of the reinforcement), an improvement of strength
can be achieved by using a fraction of the SCM material.
• PF mixture showed the highest strengths both at 14 and 28 days of curing. The relatively high
strength in mix PF indicates the presence of an inclusive and compatible mix of fibers by the
supplier. This may be further confirmed with the microscopic investigation of Mix P. The material
sample of PF mix studied under microscopy showed better dispersion and presence of finer fibers
(~15 µ).
• The bending strength tests did not show any significant improvement with the addition of fibers.
This was attributed to the small dosage of fibers and low amounts of SCM.
• Spectroscopy on the coated fibers indicated that the surface treatment procedure used in this
study successfully coated the PP fibers with SCMs.
• Recommendations for future work include using higher strength fibers at higher dosages to study
the effectiveness of fiber coating explicitly. Additionally, developing and modifying existing
methods to quantify the improvement in fiber–matrix bond interactions accurately, such as using
a core cutter method or fiber pullout method may be done. Conducting 56-day tests to allow for
complete interaction between the coated fibers and released lime to take place may also be studied.

Supplementary Materials: The following are available online at http://www.mdpi.com/2504-477X/4/2/53/s1,

Figure S1: (a) AmScope © Trinocular stereo zoom microscope setup and (b) Hitachi S-4800 FESEM.; Table S1:
polypropylene fiber properties; Table S2: chemical composition of Mix M; Table S3: chemical composition of Mix
P; Table S4: physical properties of metakaolin; Table S5: physical properties of silica fume; and Table S6: chemical
composition of the adhesive.
Author Contributions: Conceptualization, R.G.; methodology, R.B., R.G., and B.W.; software, R.B.; validation, R.B.
and B.W.; formal analysis, R.B. and B.W.; investigation, R.B.; resources, R.B.; data curation, R.B.; writing—original
draft preparation, R.B.; writing—review and editing, B.W. and R.G.; visualization, R.B. and B.W.; supervision,
R.G.; project administration, R.G.; and funding acquisition, R.G. and B.W. All authors have read and agreed to the
published version of the manuscript.
J. Compos. Sci. 2020, 4, 53 17 of 19

Funding: This research was funded by Natural Sciences and Engineering Research Council of Canada (NSERC),
grant number CRDPJ 533917-18.
Acknowledgments: Financial support of Natural Sciences and Engineering Research Council of Canada (NSERC)
is greatly appreciated. Involvement and guidance of Terry Bergen and Peter Dias from Read Jones Christoffersen
Ltd. is also acknowledged. Assistance from technical staff Armando Tura and Geoff Burton is gratefully
acknowledged. Assistance and inputs provided by Maryam Monazami is greatly appreciated. Assistance and
guidance provided by Jonathan Rudge during SEM imaging is greatly acknowledged.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Signorini, C.; Sola, A.; Malchiodi, B.; Nobili, A.; Gatto, A. Failure mechanism of silica coated polypropylene
fibres for Fibre Reinforced Concrete (FRC). Constr. Build. Mater. 2020, 236, 117549. [CrossRef]
2. Usman, M.; Farooq, S.H.; Umair, M.; Hanif, A. Axial compressive behavior of confined steel fiber reinforced
high strength concrete. Constr. Build. Mater. 2020, 230, 117043. [CrossRef]
3. Zollo, R.F. Fiber-reinforced concrete: An overview after 30 years of development. Cem. Concr. Compos. 1997,
19, 107–122. [CrossRef]
4. Nobili, A.; Lanzoni, L.; Tarantino, A.M. Experimental investigation and monitoring of a polypropylene-based
fiber reinforced concrete road pavement. Constr. Build. Mater. 2013, 47, 888–895. [CrossRef]
5. Lanzoni, L.; Nobili, A.; Tarantino, A.M. Performance evaluation of a polypropylene-based draw-wired fibre
for concrete structures. Constr. Build. Mater. 2012, 28, 798–806. [CrossRef]
6. Scrivener, K.; Crumbie, A.K.; Laugesen, P. The Interfacial Transition Zone (ITZ) Between Cement Paste and
Aggregate in Concrete. Interface Sci. 2004, 12, 411–421. [CrossRef]
7. Diamond, S.; Huang, J. The ITZ in concrete—a different view based on image analysis and SEM observations.
Cem. Concr. Compos. 2001, 23, 179–188. [CrossRef]
8. Mondal, P.; Shah, S.P.; Marks, L.D. Nanomechanical Properties of Interfacial Transition Zone in Concrete. In
Nanotechnology in Construction 3; Springer Science and Business Media LLC: Berlin/Heidelberg, Germany,
2009; pp. 315–320.
9. Felekoğlu, B.; Tosun, K.; Baradan, B. A comparative study on the flexural performance of plasma treated
polypropylene fiber reinforced cementitious composites. J. Mater. Process. Technol. 2009, 209, 5133–5144.
[CrossRef]
10. Singh, S.; Shukla, A.; Brown, R. Pullout behavior of polypropylene fibers from cementitious matrix. Cem.
Concr. Res. 2004, 34, 1919–1925. [CrossRef]
11. Cheng, K.-B.; Liu, J.-Y.; Hwang, J.-F.; Lee, M.-H.; Hsieh, C.-C. Study on the electrical and surface properties of
Polyamide 6 woven fabrics using pen-type radio frequency plasma treatment. J. Ind. Text. 2011, 41, 185–200.
[CrossRef]
12. Morent, R.; De Geyter, N.; Verschuren, J.; De Clerck, K.; Kiekens, P.; Leys, C. Non-thermal plasma treatment
of textiles. Surf. Coatings Technol. 2008, 202, 3427–3449. [CrossRef]
13. Trejbal, J.; Nežerka, V.; Somr, M.; Fladr, J.; Potocký, Š.; Artemenko, A.; Tesarek, P. Deterioration of bonding
capacity of plasma-treated polymer fiber reinforcement. Cem. Concr. Compos. 2018, 89, 205–215. [CrossRef]
14. Arias, J.P.M.; Vazquez, A.; Escobar, M.M. Use of sand coating to improve bonding between GFRP bars and
concrete. J. Compos. Mater. 2012, 46, 2271–2278. [CrossRef]
15. Guglielmi, M. Sol-gel science. Mater. Chem. Phys. 1990, 26, 211–212. [CrossRef]
16. Bakera, A.T.; Alexander, M.G. Use of metakaolin as supplementary cementitious material in concrete, with
focus on durability properties. RILEM Tech. Lett. 2019, 4, 89–102. [CrossRef]
17. Badogiannis, E.; Sfikas, I.; Voukia, D.V.; Trezos, K.G.; Tsivilis, S.G. Durability of metakaolin Self-Compacting
Concrete. Constr. Build. Mater. 2015, 82, 133–141. [CrossRef]
18. Guo, Z.; Jiang, T.; Zhang, J.; Kong, X.; Chen, C.; Lehman, D.E. Mechanical and durability properties of
sustainable self-compacting concrete with recycled concrete aggregate and fly ash, slag and silica fume.
Constr. Build. Mater. 2020, 231, 117115. [CrossRef]
19. Khatri, R.; Sirivivatnanon, V.; Gross, W. Effect of different supplementary cementitious materials on
mechanical properties of high performance concrete. Cem. Concr. Res. 1995, 25, 209–220. [CrossRef]
20. Lothenbach, B.; Scrivener, K.; Hooton, R. Supplementary cementitious materials. Cem. Concr. Res. 2011, 41,
1244–1256. [CrossRef]
J. Compos. Sci. 2020, 4, 53 18 of 19

21. Ping, X.; Beaudoin, J. Modification of transition zone microstructure—Silica fume coating of aggregate
surfaces. Cem. Concr. Res. 1992, 22, 597–604. [CrossRef]
22. Mindess, S. Bonding in Cementitious Composites: How Important is it. MRS Proc. 1987, 114, 3. [CrossRef]
23. Cheng-Yi, H.; Feldman, R. Hydration reactions in portland cement-silica fume blends. Cem. Concr. Res. 1985,
15, 585–592. [CrossRef]
24. Ganesh, Y.S.V.; Durgaiyya, P.; Shivanarayana, C.; Prasad, D.S.V. Compressive strength of concrete by partial
replacement of cement with metakaolin. In Proceedings of the International Conference on Functional
Materials, Characterization, Solid State Physics, Power, Thermal and Combustion Energy: FCSPTC-2017,
Andhra Pradesh, India, 7–8 April 2017; Volume 1859, p. 20059.
25. Narmatha, M.; Felixkala, T. Meta kaolin–The Best Material for Replacement of Cement in Concrete. IOSR J.
Mech. Civ. Eng. 2016, 13, 66–71. [CrossRef]
26. Chu, S.; Kwan, A. Co-addition of metakaolin and silica fume in mortar: Effects and advantages. Constr.
Build. Mater. 2019, 197, 716–724. [CrossRef]
27. Paiva, H.; Silva, A.M.D.S.; Velosa, A.; Cachim, P.; Ferreira, V. Microstructure and hardened state properties
on pozzolan-containing concrete. Constr. Build. Mater. 2017, 140, 374–384. [CrossRef]
28. Poon, C.; Kou, S.; Lam, L. Compressive strength, chloride diffusivity and pore structure of high performance
metakaolin and silica fume concrete. Constr. Build. Mater. 2006, 20, 858–865. [CrossRef]
29. Gupta, R. US Patent for Surface Treatment for Concrete Reinforcement Patent. U.S. Patent 9,908,813,
6 March 2018.
30. Wang, B.; Gupta, R.; Dias, P.; Bergen, T. Coefficient of Permeability of Cement-based Repair Materials. In
Proceedings of the First International Conference on New Horizons in Civil Engineering, Victoria, BC,
Canada, 25–27 April 2018; p. 8.
31. Al-Zahrani, A.M.; Maslehuddin, M.; Al-Dulaijan, S.; Ibrahim, M. Mechanical properties and durability
characteristics of polymer- and cement-based repair materials. Cem. Concr. Compos. 2003, 25, 527–537.
[CrossRef]
32. Durability Performance of Repaired Reinforced Concrete Beams. ACI Mater. J. 1994, 91. [CrossRef]
33. Fibermesh- Concrete Solutions by Propex, “Fibermesh150-12mmDatasheet.pdf”. Available online:
http://www.rindler-gmbh.at/data-rindler/uploads/hotlinks_appfilelink/Fibermesh150-12mmDatasheet.pdf
(accessed on 26 January 2020).
34. Burgess Pigment, “Calcined Aluminum Silicate”. Available online: https://www.burgesspigment.com/tds/
burgess-optipozz/?pdf=true (accessed on 26 January 2020).
35. Kryton International Inc. “TDS-Con-Fume.pdf”. Available online: https://www.kryton.com/technical-info/
technical-data-sheets/TDS-Con-Fume.pdf (accessed on 26 January 2020).
36. 3M, “Safety Data Sheet: 3M(TM) Super 77(TM) Multipurpose Adhesive (Aerosol)”.
Available online: https://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_
zu8l00x482xN8mvNv70k17zHvu9lxtD7SSSSSS-- (accessed on 26 January 2020).
37. C01 Committee Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50-mm]
Cube Specimens). ASTM Int. 2016. [CrossRef]
38. D01 Committee Test Method for Tensile Strength of Chemical-Resistant Mortar, Grouts, and Monolithic
Surfacings. ASTM Int. 2018. [CrossRef]
39. Wild, S.; Khatib, J.; Jones, A. Relative strength, pozzolanic activity and cement hydration in superplasticised
metakaolin concrete. Cem. Concr. Res. 1996, 26, 1537–1544. [CrossRef]
40. Dinakar, P.; Sahoo, P.K.; Sriram, G. Effect of Metakaolin Content on the Properties of High Strength Concrete.
Int. J. Concr. Struct. Mater. 2013, 7, 215–223. [CrossRef]
41. Wild, S.; Khatib, J. Portlandite consumption in metakaolin cement pastes and mortars. Cem. Concr. Res. 1997,
27, 137–146. [CrossRef]
42. Khatib, J.; Baalbaki, O.; Elkordi, A.A. Metakaolin. In Waste and Supplementary Cementitious Materials in
Concrete; Elsevier BV: Amsterdam, The Netherlands, 2018; pp. 493–511.
43. Gameiro, A.; Silva, A.M.D.S.; Faria, P.; Grilo, J.; Branco, T.; Veiga, M.D.R.D.S.; Velosa, A. Physical and
chemical assessment of lime–metakaolin mortars: Influence of binder:aggregate ratio. Cem. Concr. Compos.
2014, 45, 264–271. [CrossRef]
44. Zou, D.; Li, K.; Xie, S.; Liu, Y.; Ren, W.; Shi, L.; Liu, Z. Feasibility of assessing segregation in internally cured
mortar based on the variation of properties. Constr. Build. Mater. 2017, 147, 750–757. [CrossRef]
J. Compos. Sci. 2020, 4, 53 19 of 19

45. Qian, X.; Li, Z. The relationships between stress and strain for high-performance concrete with metakaolin.
Cem. Concr. Res. 2001, 31, 1607–1611. [CrossRef]
46. Ahmed, T.A.H.; Daoud, O.M.A. Influence of Polypropylene Fibres on Concrete Properties. IOSR J. Mech. Civ.
Eng. 2016, 13, 9–20. [CrossRef]
47. Ibrahim, Y.A.; Maroof, N.R.; Abdulrahman, A.R. Influence of Polypropylene Fibre on Strength and Workability
Properties of Cement Mortar. In Proceedings of the 2019 International Engineering Conference (IEC), Erbil,
Iraq, 23–25 June 2019; pp. 221–226.
48. Menshaz, A.M.; Johari, M.A.M.; Ahmad, Z.A. Characterization of metakaolin treated at different calcination
temperatures. In Proceedings of the International Conference of Global Network for Innovative Technology
and Awam International Conference in Civil Engineering (Ignite-Aicce’17): Sustainable Technology
And Practice For Infrastructure and Community Resilience, Penang, Malaysia, 8–9 August 2017; Volume 1892,
p. 20028.

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