Effects of Cement–Polymer Interface Properties

on Mechanical Response of Fiber-Reinforced

Cement Composites
Sina Askarinejad, S.M.ASCE 1; and Nima Rahbar, M.ASCE 2

Abstract: Cement is one of the most consumed materials in the world. The cement industry is responsible for a large portion of global carbon
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dioxide emissions. Cement production and therefore carbon dioxide emissions can be decreased by increasing the durability and enhancing
the mechanical properties of cement-based materials. On the other hand, an important weakness of concrete is its weak tensile properties,
which are the main reasons for its failure and low durability. Therefore, over the past 30 years, many studies have focused on improving
tensile properties using a variety of physical and chemical methods. One of the most successful attempts is to use polymer fibers in the
structure of concrete to obtain a composite with high tensile strength and ductility. However, a thorough understanding of the mechanical
behavior of fiber-reinforced concrete requires knowledge of fiber cement interfaces at the nano scale. In this study, a combination of ex-
perimental and molecular dynamics (MD) techniques is used to study the nanostructure of fiber cement interfaces. Scanning electron micros-
copy (SEM) and energy-dispersive X-ray spectroscopy (EDX) analysis are used to obtain a better understanding of the C-S-H fiber (in cement
chemistry notation, C = CaO, S ¼ SiO2 , and H ¼ H2 O) interfaces. The results show that the C/S ratio changes in the interface
of cement and polymeric fibers and is largely affected by the functional group of the polymers. The results are then used to propose a
more realistic molecular dynamics model for C-S-H in the vicinity of the three most used polymeric fibers: polypropylene, polyvinyl alcohol,
and nylon-6. The full atomistic simulations show that the molecular structure of C-S-H at the interface depends on the properties of the
polymer functional group. The adhesion energy between the polymeric fibers and the relevant C-S-H structure is then computed using
atomistic simulations. The adhesion energy between C-S-H and polymers increases with the polarity of the fiber. The mechanical response
of cement paste with added polymeric fibers is then experimentally studied using the split-cylinder test. The experimental results further
show that the adhesion energies between the fibers and cement increase as a function of the polarity of the fibers. DOI: 10.1061/(ASCE)
NM.2153-5477.0000119. © 2017 American Society of Civil Engineers.
Author keywords: C-S-H; Polymeric fibers; Interface; Energy-dispersive X-ray spectroscopy (EDX) mapping.

Introduction
The cement-based matrix of concrete has a complex structure
that makes concrete a weak material in terms of material properties
such as tensile strength and toughness. Therefore, many studies
have focused on improving the tensile properties of concrete using
a variety of physical and chemical methods (Balaguru and Shah
1992). One of the most successful attempts is to use polymeric ma-
terials in the structure of concrete to obtain a composite with high
tensile strength and ductility (Abbasnia et al. 2013; Akihama et al.
1985; Betterman et al. 1995; Garcia et al. 1997; Li et al. 1994).
Polypropylene, polyvinyl alcohol (PVA), and nylon-6 are some
of the most used polymeric fibers in this application. They also
represent a range of fibers with polar to nonpolar functional groups.
Improving the performance of polymer fiber-reinforced cement
composites can also increase the durability of cement-based struc-
tures. Producing stronger and more durable cement-based materials
1
Dept. of Mechanical Engineering, Worcester Polytechnic Institute,
Worcester, MA 01609.
2
Associate Professor, Dept. of Civil and Environmental Engineering,
Worcester Polytechnic Institute, Worcester, MA 01609 (corresponding
author). E-mail: nrahbar@wpi.edu
Note. This manuscript was submitted on February 17, 2016; approved
on October 31, 2016; published online on February 7, 2017. Discussion
period open until July 7, 2017; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Nanomechanics
and Micromechanics, © ASCE, ISSN 2153-5434.
would decrease the need for cement production and therefore
decrease carbon dioxide emissions (Van Vliet et al. 2012).
To improve the mechanical performance of concrete and other
cement-based composites, cement material and chemical composi-
tions need to be characterized, well understood, and then improved.
In portland cement, the raw materials are limestone and clay.
Hence, a typical composition of portland cement is approximately
67% calcium oxide (CaO) and 22% silicon dioxide (SiO2 ), with
mainly alite and belite molecules. The products of the cement hy-
dration reaction are mainly portlandite and calcium silicate hydrate,
or C-S-H gel. The C-S-H gel is up to 70% of the final volume.
The produced C-S-H gel from the hydration reaction is respon-
sible for the cohesion and strong mechanical properties of cement
pastes (Dolado et al. 2007). An understanding of the nature of chemi-
cal reactions occurring in C-S-H is also necessary in modeling the
mechanical properties of concrete at the nano scale. To understand
the chemical reactions in C-S-H, many researchers have previously
tried to characterize the structure of C-S-H gel at the atomistic
level (Hajilar and Shafei 2015; Hamid 1981; Richardson 2008;
Shahsavari et al. 2011; Shalchy and Rahbar 2015b; Taylor 1993).
In that regard, different strategies were used to model the atomistic
structure of C-S-H to understand its nanostructure properties
(Richardson 2004; Wu et al. 2011). Bauchy et al. (2014) constructed
a tobermorite crystalline structure, a more realistic C-S-H, and an
artificial ideal glass. They showed that although C-S-H retains some
signatures of a tobermoritelike layered structure, hydrated species
are completely amorphous. Earlier, Pellenq et al. (2009) proposed

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 a molecular model for C-S-H gel with the stoichiometry of ðCaOÞ1.65
(SiO2 ) ðH2 OÞ1.73 . In a more recent study, Qomi et al. (2014) inves-
tigated the effect of the C/S ratio on the molecular structure of C-S-H
using the molecular dynamics (MD) simulation technique.
In a study by Soyer-Uzun et al. (2012), X-ray diffraction (XRD)
was used to investigate the atomistic structure of C-S-H considering
the coordinate number of Ca-O. They believed C-S-H is an evolu-
tion of a tobermorite-like structure to a jennite-like structure. Allen
(a)
et al. (2007) measured the mean formula and solid density of
nanoscale C-S-H gel particles by combining small-angle neutron
and X-ray scattering data [ðCaOÞ1.7 ðSiO2 Þ ðH2 OÞ1.8 and d ¼
2.604 ðg=cm3 Þ ].
Understanding the mechanical behavior of fiber-reinforced con-
crete requires thorough knowledge of the fiber matrix interface
structure. During the past decade, the principal new data bearing
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on the structure of the polymer cement interface have been on com-

positions determined by X-ray microanalysis and on silicate anion
structures (Yu et al. 1999). Although a large body of microscopic
studies has been performed on the interfaces present in fiber-
reinforced cement-based composites (Bentur and Mindess 2006;
Sakulich and Li 2011), the nanostructure of the interfaces between
cement and polymer fiber has not been thoroughly investigated.
This understanding is needed to fully predict and improve the
mechanical properties of fiber-reinforced cement-based composites
because the fibers change the chemical reactions and chemical pro-
ductions of hydration reaction. Moreover, multiscale studies need
to be performed to connect the atomic- and nanoscale properties of
the materials to the macroscale properties.
This study presents combined small-scale numerical and exper-
imental studies on the properties of polymer cement interfaces
and their effect on the overall mechanical properties of fiber-
reinforced cement paste. In this study, scanning electron microscopy
and energy-dispersive X-ray spectroscopy (SEM/EDX) analysis is
initially used to investigate C-S-H atomic composition in the vicinity
of three typical polymer fibers, polypropylene, polyvinyl alcohol,
and nylon-6. Then, molecular dynamics models of the interaction
between the polymers and the relevant C-S-H structure are con-
structed, and the adhesion energies are calculated. Finally, split-
cylinder test is performed on the polymer-reinforced cement paste.
A correlation between the load-displacement curves and the adhe-
sion energies is found.
Materials and Methods
Fiber Matrix Interface Characterization by SEM and
EDX
Three polymeric fibers were used to make fiber-reinforced cement
paste. The first two polymer fibers, PVA and nylon-6 with the
International Union of Pure and Applied Chemistry (IUPAC) names
of polyvinyl alcohol and poly(hexano-6-lactam), respectively, have
polar side chains with different polarities. The third polymer fiber is
polypropylene, which has a nonpolar side chain. The same func-
tional group usually undergoes the same or similar chemical reac-
tion(s) regardless of the size of its molecule (McNaught et al. 1997).
The goal is to observe how the polarity of the side chains affects the
nanostructure of the fiber cement interface.
Nylon-6 has amide groups [Fig. 1(a)], which have the highest
polarities among other functional groups. It has two different high
electronegative atoms in its structure: the oxygen and nitrogen
atoms in the amide group. Both oxygen and nitrogen contribute to
hydrogen bonding. Nitrogen atoms are hydrogen bond acceptors or
donors, and oxygen atoms are hydrogen bond acceptors. PVA is one
of the most common fibers that have been used in fiber-reinforced
(b) (c)
Fig. 1. Monomer formulas for the three different polymers used as
fibers in cement paste are shown in this picture: (a) monomer for
nylon-6; (b) monomer of PVA; (c) monomer of polypropylene; it
can be observed that nylon-6 has a midside chain on its monomer,
whereas PVA has hydroxyl groups; polypropylene’s macromolecule
is mainly nonpolar
cement composites. PVA is from the alcohol group, which has
hydroxyl side chains [Fig. 1(b)]. On the one hand, this functional
group has less polarity than the amide group, but on the other hand,
the alcohol functional group has just one oxygen atom that contrib-
utes to hydrogen bonding. Oxygen atoms in the hydroxyl group are
hydrogen bond acceptors or donors. The last polymer, polypropyl-
ene, is composed of alkanes [Fig. 1(c)]. Alkanes have little intermo-
lecular association because the carbon-hydrogen bond is nonpolar.
Alkanes are essentially nonpolar molecules and insoluble in water.
All fibers were provided by the FORTA Corporation (Grove City,
Pennsylvania).
The fiber-reinforced cement pastes evaluated in this study were
prepared by mixing polymer fibers, water, and cement powder to
obtain mixtures with a specific concentration of fibers for a specific
composition of cement. A water-to-cement ratio of 0.4 was used for
all the samples. The cement paste ingredients were mixed with a
blender. All samples had 1% volume of polymeric fibers. The fol-
lowing procedure was used for the preparation of the cement pastes:
first, the weight percentages of cement, fiber, and water were mea-
sured in different bowls; then, the cement was mixed at a medium
speed for 15 s; water and fibers were added to the cement gradually,
and they were mixed for 90 s. A spatula was used to scrape the wall
and bottom of the bowl, and another 90 s of mixing was done at
medium speed. After the mixing was complete, the fresh cement
pastes were cast in plastic cylinders 5.1 cm in diameter and
10.2 cm in height and sealed at 23  1°C for curing in a curing
room. At the age of 24  1 h, the cylinder samples were demolded.
Any excess of moisture on the surface was removed with a towel,
and the specimens were sealed in plastic bags at 23  1°C until the
age of testing. To ensure desired compressive strength, the samples
were tested after 28 days, then cut using a diamond cutter and
polished to be prepared for the SEM/EDX analysis.
Molecular Modeling of C-S-H Gel and Polymers
To have a better understanding of C-S-H at the nano scale, H. F. W.
Taylor’s postulate was used to begin the atomistic modeling

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 (Taylor 1993). C-S-H gel is mostly made of tobermorite and jennite
(Bauchy et al. 2014). Tobermorite has the chemical formulation
of Ca5 Si6 O16 ðOHÞ2 · 7H2 O, with a C/S ratio of 0.83 and density
of 2.18 g=cm3 , whereas jennite has the chemical formulation of
Ca9 ðSi6 O18 Þ6 · 8H2 O, with a C/S ratio of 1.5 and density of
2.27 g=cm3 . Moreover, the C/S ratio in C-S-H varies from 0.7
to 2.3, and its density is approximately 2.6 g=cm3 (Pellenq et al.
2008). Using this information and the data obtained from the
EDX mapping of the C-S-H gel in the vicinity of polymeric fibers,
a more realistic model for C-S-H can be proposed. This approach
can be used to investigate the adhesion energies and other interface
properties of fiber-reinforced cement composites (Shalchy and
Rahbar 2015a).
The selection of a force field that results in an accurate model for
the potential energy hypersurface in which the nuclei moves is an
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important step in performing atomistic simulations. In general, the
potential energy consists of valence, cross-term, and nonbonded
energies (Sun 1998; Sun et al. 1998)
Etotal ¼ Evalence þ Ecross-term þ Enonbonded ð1Þ
In Eq. (1), a bond-stretching term, a bending energy term, and
four body terms, including a dihedral bond-torsion angle term and
an inversion (out-of-plane interaction) term, contribute to the va-
lence energy. The cross-term energy Ecross-term accounts for the en-
ergy induced by the changes in the bond length and the bond angle
with the surrounding atoms. Enon-bonded , the nonbonded term, con-
sists of intermolecular and intramolecular interaction. The non-
bonded terms include hydrogen bonds (H-bonds) and van der
Waals (vdW) interactions that are induced dipole-dipole interac-
tions (also known as London forces). Moreover, the Coulomb
interaction accounts for electrostatic interaction.
The condensed-phase optimized molecular potentials for
atomistic simulation studies (COMPASS) (Sun 1998) force field
was used for this calculation. It is a powerful force field for atom-
istic simulation of condensed materials and one of the first ab
Fig. 2. Schematic of the initial molecular model of C-S-H
© ASCE 04017002-3
J. Nanomech. Micromech., 2017, 7(2): 04017002
initio–based force fields that is parameterized and validated with
the experiment results (Sun 1998). Therefore, it is an accurate
and reliable force field for predicting the mechanical, structural,
and thermodynamic properties of a vast range of molecules and
atoms and can be used to study the nanomechanical properties of
the interface (Grujicic et al. 2007; Lu and Dunn 2010; Salahshoor
and Rahbar 2012). The unit cells of C-S-H gel were created and
optimized. The simulations were performed at room temperature
(25°C). In this study, the structure of jennite proposed by Hamid
(1981) was used to initiate the basic molecular model of C-S-H
(Hamid 1981). However, in our model, it was assumed that the in-
terlayer Ca2þ ions react with water and produce hydroxyl ions.
Hence, the structure that was proposed here was made of SiO2 ,
Ca2þ , and CaðOHÞ2 layers arranged as shown in Fig. 2. Afterwards,
multiple Si atoms were randomly omitted, and multiple Ca2þ atoms
were added to the structure for the following reasons: (1) to satisfy
the C/S ratio in the C-S-H structure at the interface with different
polymer fibers, (2) to satisfy the overall charge balance in the
system, and (3) to provide the necessary defects in the structure of
C-S-H. This approach was applied to construct different C-S-H
models with different C/S ratios using the EDX analysis results.
The layered structure of the C-S-H surface was modeled and the
potential energy was optimized using the steepest descent approach
followed by the conjugate gradient method. The dimensions of the
system were 40 × 40 × 45 Å. The charge distribution was calcu-
lated using the QEq method (Rappe and Goddard III 1991). The
nonbonded summations were calculated using Ewald for electro-
static interaction with an accuracy of 0.001 kcal=mol. Based on
each atom charge with the truncation of atoms further than the
cut-off distance of 15.5 Å, the charge distribution for van der Waals
interaction was computed (Fig. 3).
To model the polymer fiber macromolecules, monomers of the
chosen polymers (vinyl alcohol, propylene, and hexano-6-lactam)
were initially constructed. Chains of PVA, polypropylene, and ny-
lon-6 were then created by assembling 100-monomer units of vinyl
alcohol, propylene, and hexano-6-lactam, respectively (Gujrati and
Leonov 2010).
Five possible structures of each prescribed polymer molecule
with the desired density of 1.2 g=cm3 at 298 K were created
and energetically optimized. Each configuration was then subjected
Fig. 3. Molecular model of C-S-H after optimization
J. Nanomech. Micromech.
 to molecular dynamics simulation to let the atoms relax down to
the minimum energy in the structure (Hossain et al. 2010). Initially,
the canonical (constant volume constant temperature, NVT) dy-
namics were carried out for 60 ps by 1.0 fs time steps at 300 K,
followed by the isothermal-isobaric (constant pressure constant
temperature, NPT) dynamics compressed at high pressure
(5000 bar) for 120 ps at 300 K. Next, NVT molecular dynamics
were applied at 600 and 300 K, successively, for approximately
50 and 70 ps, respectively. Subsequently, 120 ps molecular dynam-
ics were performed in the NPT ensemble at 1 bar, and the resulting
density was compared to the experimental value. If the density was
lower than the experimental density, the first two steps were re-
peated. Finally, molecular dynamics simulation was performed
in the NVT ensemble at 1 bar for 300 ps (Youssefian et al. 2015).
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Mechanical Testing
There are different approaches to predict, analyze, and improve the
tensile and compressive strength of cement-based composites
(Misra and Poorsolhjouy 2015). The tensile strength of concrete
is an important parameter in the design of civil engineering struc-
tures. To determine the tensile strength of concrete for existing
structures, different experiments are essential. Compression tests
are very common to investigate the compressive strength of con-
crete and fiber-reinforced concrete samples. Because of the com-
plex nature of uniaxial tension tests, splitting tension tests are
usually carried out on cylindrical specimens or cores. In this study,
a split testing setup was chosen because of the fiber-pullout effect
on the polymeric fibers, which is influenced by the polymers’
molecular structures.
To compare the mechanical properties of fiber-reinforced ce-
ment paste and investigate the effect of different polymeric fibers
in these composites and their molecular-level interactions, numer-
ous samples were prepared. Nine samples each of the control, ce-
ment and PVA, cement and nylon-6, and cement and polypropylene
batches were prepared. Three samples from each batch were tested
at 3, 7, and 28 days. The fibers shape was identical. Nineteen-
mm-long and 175-μm-thick cylindrical polymeric fibers were used.
30 µm
Fiber/ Matrix
Interface
Nylon-6 fiber
(a)
50 µm 30 µm
PVA fiber Polypropylene fiber
(b) (c)
Fig. 4. SEM images of fiber matrix interfaces for the (a) nylon-6;
(b) PVA; (c) polypropylene; regions of fiber matrix interfaces are in-
dicated in the image
© ASCE
J. Nanomech. Micromech., 2017, 7(2): 04017002
The split-cylinder test is an indirect way to determine the tensile
strength of concrete samples. This test was chosen to investigate the
effect of the polarity of polymers’ functional group and adhesion
energy between fiber and cement paste. In other words, the first
movement of fibers in the structure of the composite can be cap-
tured using this test. In this test, a standard test cylinder (length
101 mm and diameter 51 mm) was placed horizontally between
the loading surfaces of the compression test machine. A load
was applied uniformly along the length of the sample and caused
a crack along the diameter of the cylinder. If an element on the
diameter of the sample is assumed in addition to a pair of compres-
sion load, a pair of the tension load is applied to the element
perpendicular to the loading direction.
Assuming elastic behavior for the concrete, the tensile stress
acting on the vertical plane on the diameter of the cylinder can
be calculated as
2P
σ¼ ð2Þ
πDL
where P = compression force; D = diameter of the cylinder; and L
= length of cylinder.
Results and Discussion
SEM and EDX Interface Characterization
Typical SEM images of the polymer fiber, matrix, and polymer ma-
trix interfacial transition zones for all three types of polymer fibers
are shown in Fig. 4. The SEM images of the samples clearly show
there is a transition zone between the polymer fibers and cement
paste. These figures show the interfacial layer between fiber and
matrix has a thickness of approximately 1–5 μm around the fiber.
Regions of fiber, cement matrix, unhydrated cements, and fiber ma-
trix interface are also indicated in the figure. The EDX results and
analysis for three different fiber cement interfaces are shown in
Fig. 5. X-ray mapping is used to investigate the distribution and
density of existing elements such as Si and Ca in the area around
each fiber. The X-ray mappings of the Si and Ca elements for ny-
lon-6 and PVA fibers clearly show the accumulation of calcium at
the fiber matrix interface, which is represented by a circle in the
figures. However, this phenomenon is not observed in the samples
with nonpolar polypropylene fibers. Moreover, the EDX is per-
formed on 10 spectra of the fiber matrix interface and 10 of regular
C-S-H gel. The numerical EDX results show that the ratio of
C/S in the interfacial zone significantly changes for PVA and ny-
lon-6 fibers, whereas it remains almost constant for polypropyl-
ene fibers, shown in Fig. 6. The ratio of C/S in the interfacial
transition zone between PVA and nylon-6 fibers and cement in-
creases in comparison to the regular C-S-H in fiber-reinforced
composite matrices. Furthermore, this ratio does not change for
polypropylene fibers. This can be due to the polarity of different
fibers caused by the functional groups on their molecular
structure.
C-S-H Gel Polymer Interface at the Atomic Scale
The complex atomistic model of C-S-H gel can be verified by
important stoichiometric parameters such as the C/S ratio and
the first- and second-order thermodynamic quantities, such as
density and Young’s modulus. The thermodynamic properties of
C-S-H are obtained to assess the suitability of the force field to
model the C-S-H gel. The densities of C-S-H from the molecular
dynamics and experiments are estimated to be approximately 2.410
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Nylon-6 PVA Polypropylene

Fig. 5. EDX X-ray map results for three polymeric fibers in the C-S-H matrix; the results show that the Ca2þ ions are absorbed on the interface of
nylon-6 and PVA fibers, but the interface of polypropylene fiber has not significantly changed

and 2.64 ðg=cm3 Þ, respectively. The modulus of elasticity is esti- stress is commonly used to relate the computed stress in molecular
mated to be 57.02, 24.52, and 22.20 GPa in the x, y, and z-direc- dynamics to continuum stresses. The Young’s moduli is then com-
tions (shown in Fig. 3), respectively. Two different methods are puted as the average of the three initial stress-strain slopes after
used to calculate the elastic moduli. In the first method, the struc- relaxation. In the second method, Young’s moduli are indirectly
ture is stretched in all three directions to the maximum strain am-
plitude of 0.01 in 10 steps, and virial stresses are computed. Virial
Table 1. Adhesion Energy (J=m2 ) between Polymers and the Relevant
C-S-H Gel
Polymer Adhesion energy
Polypropylene 64.18
PVA 89.91
Nylon-6 95.48

Fig. 6. Comparison of the EDX results between atomic percentage of

Ca and Si elements on samples of regular C-S-H gels and EDX results
on samples of polymer C-S-H gel interfaces; 10 EDX spectra are used Fig. 7. Typical broken fiber-reinforced cement paste sample subjected
for each sample to split-cylinder test

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 25,000
where L0 = initial length of the unit cell in the desired direction,
L = final length, and U = the energy of the system after increasing
20,000 the length. It is observed that both methods result in almost the
same values, 32.8 and 34.2 GPa for the suggested C-S-H model,
which matches the experimental data in the literature well
15,000 (Manzano et al. 2007, 2009). The Poisson’s ratio of C-S-H is cal-
Load (N)

culated to be 0.29, which is also similar to the experimental results

(Constantinides and Ulm 2004).
10,000
The constructed models are further used to calculate the adhe-
sion energy between the polymers and the C-S-H gel. According to
5,000 Cement Paste the findings in the SEM/EDX analysis, presented previously, the
nanostructure of the C-S-H model in the vicinity of each polymer
Cement Paste + Polypropylene fibers
is different.
0 To measure the adhesion energies between the polymers and the
0 1 2 3 4 5
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C-S-H gel, models are constructed by placing polymer chains

Displacement (mm)
on the C-S-H surface models in a super-cell. A large vacuum (50 Å)
Fig. 8. Typical failure of cement paste and fiber-reinforced cement is added above the polymer so interaction with both sides of the
paste C-S-H gel due to the periodic boundary condition is avoided. Five
different configurations of each chain of polymer are chosen as a
confined layer on top of the C-S-H gel. Then, the polymer layers
are positioned on top of the C-S-H layer and the whole system is
computed from molecular dynamic simulation for each direction by optimized to compute the minimum energy of the system. This is
the following equation: followed by the molecular dynamic simulation of the system under
  the NVT ensemble at a temperature of 298 K for a period of 1 ps.
U E L − L0 The presence of Ca2þ ions makes the system charged; therefore,
¼ ð3Þ
A×L 2 L0 the QEq method (Rappe and Goddard III 1991) was used to

30,000 30,000

25,000 25,000

20,000 20,000
Load (N)
Load (N)

15,000 15,000

10,000 10,000

5,000 5,000
Polypropylene PVA
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

(a) Displacement (mm) (b) Displacement (mm)

30,000

25,000

20,000
Load (N)

15,000

10,000

5,000
Nylon-6
0
0 1 2 3 4 5
(c) Displacement (mm)

Fig. 9. Load-displacement curve for cement paste with added fibers cured for 3 days

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 redistribute the overall charge on the atoms in the current atomistic
model. After energy optimization of the cell, 120 ps of dynamic
simulations with 1 fs time steps are performed. This time period
is enough for the systems to reach convergence and energy stability.
In this step of the simulation, the charge is set to 0 to eliminate
the effect of charges resulting from the Ca2þ ions in the system.
Furthermore, to eliminate the effect of temperature on the adhesion,
the simulations are performed at room temperature. The interaction
energy (Einteraction ) between the polymer molecules and the C-S-H
surface is calculated using the following equation:
Einteraction ¼ ðEC-S-H þ Epolymer Þ − Etotal
where Einteraction = interaction energy of the system; Etotal = total
energy of the C-S-H surface and the polymer molecules in equilib-
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Table 1. Adhesion energy between PVA, polypropylene, and
nylon-6 and the relevant C-S-H gel is computed as 89.91, 95.48,
and 64.18 kJ=m2 , respectively. The variation in the computed
adhesion energies is due to the presence of functional groups
and hence different polarities of the polymer molecules. The func-
tional groups affect the adhesion energy primarily by changing the
C/S ratio of the C-S-H at the interface and further by absorbing
additional positive ions in the C-S-H structure.
Mechanical Testing
ð4Þ
A typical broken sample after the split-cylinder test is shown in
Fig. 7. The long fibers can be observed in the image. From this
image, three main failure steps are implied: failure of cement paste,

rium; EC-S-H = energy of the surface without the polymer; and
Epolymer = energy of the polymer without the surface, both separated
in vacuum in equilibrium (Kisin et al. 2007). As shown in the EDX
analysis, the C/S ratio in the C-S-H gel increases for polymer ce-
ment interfaces with polar fibers. The polarity of polymer fibers
enhances the absorption of water molecules and positive ions, such
as Ca2þ , during hardening of the fiber molecules. Hence, a more
realistic adhesion energy for the polymer cement interface in each
type of fiber-reinforced concrete can be calculated using the actual
C/S ratio in the C-S-H gel. The final interaction energies and the
computed adhesion energies between PVA, polypropylene, and
nylon-6 and the relevant C-S-H gel model are presented in
fiber detachment or debonding, and fiber pull-out continuation. The
first occurs in the failure of the tensile strength of the cement paste;
the second is when the stress in the sample exceeds the strength of
the interface between the fibers and cement paste, which is affected
by the polarity of the polymers’ functional groups; and the third
occurs due to the friction between fibers and cement paste, which
is affected by fiber roughness.
The failure strength of fiber-reinforced cement paste can be ob-
tained from testing control samples. A typical load-displacement
graph of a cement paste sample with no additive and a sample
with polymeric fibers is shown in Fig. 8. In the samples with fibers,
the last step of failure strongly depends on the roughness of the

35,000
35,000
30,000
30,000

25,000
25,000
Load (N)

Load (N)

20,000
20,000

15,000
15,000

10,000 10,000

5,000 5,000
Polypropylene PVA
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0 1 2 3 4 5
(a) Displacement (mm) (b) Displacement (mm)

35,000

30,000

25,000
Load (N)

20,000

15,000

10,000

5,000
Nylon-6
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
(c) Displacement (mm)

Fig. 10. Load-displacement curve for cement paste with added fibers cured for 7 days

© ASCE 04017002-7 J. Nanomech. Micromech.

J. Nanomech. Micromech., 2017, 7(2): 04017002

 40,000 40,000

35,000 35,000

30,000 30,000

25,000 25,000
Load (N)

Load (N)
20,000 20,000

15,000 15,000

10,000 10,000

5,000 5,000
PVA
Polypropylene
0 0
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0 1 2 3 4 5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

(a) Displacement (mm) (b) Displacement (mm)

40,000

35,000

30,000

25,000
Load (N)

20,000

15,000

10,000

5,000
Nylon-6
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
(c) Displacement (mm)

Fig. 11. Load-displacement curve for cement paste with added fibers cured for 28 days

fibers at the nano and micro scales. However, there is a correlation is always challenging and quite important. The results of this study
between the second step of failure and the adhesion energies show there is a correlation between the yield load of fiber-
between the polymers and the relevant C-S-H model. The reinforced cement paste and the polarity of functional groups in
force corresponding to this point is called the yield load in the chemical composition of the polymeric fibers.
this study.
Fig. 9 shows the load-displacement behavior of tested samples
on the third day. The circles in the graphs show the second step of
failure. The yield load is higher for cement and nylon-6 samples
than for cement and PVA samples, and it is higher for cement
and PVA samples than for cement and polypropylene samples.
Figs. 10 and 11 show the tested samples at 7 and 28 days. The same
trend for the yield load can be observed in the samples.
The yield loads for samples with PVA and polypropylene are
close; however, the load for samples with nylon-6 fibers is mark-
edly higher. To conclude, the graphs can be summarized in Fig. 12.
These results agree well with the experiments done by Song
et al. (2005).
The implications of these results are quite significant. First, they
show that the polymers’ chemical composition and functional
groups change the structure of C-S-H gel in the vicinity of the pol-
ymers. This result is important first because changing the chemical
structure and C/S ratio of C-S-H gel affects the overall mechanical
response of fiber-reinforced cement paste, and second, the ion
transfers during the hydration reaction may affect the corrosion
in the composite, especially if there are other reinforcing materials
in the composite. The correlation between the atomic-scale and
Fig. 12. Summary of the split-cylinder test results
nanoscale properties with the macroscale properties of materials

© ASCE 04017002-8 J. Nanomech. Micromech.

J. Nanomech. Micromech., 2017, 7(2): 04017002

 Conclusion
Polymer fibers are widely added to concrete to enhance tensile
properties and ductility. Although there is a large body of data
on this subject, the nanostructure and nanomechanical properties
of the polymer fiber cement interface, which is pivotal in the design
of robust polymer reinforced concrete, are still not completely
known. This study presents a SEM/EDX analysis to investigate
the nanostructure of the cement fiber interface and the correspond-
ing mechanical properties. In this study, three different polymer fi-
bers are used based on the polarity of their functional groups. The
electron microscopy results show the ratio of C/S changes in the
fiber matrix interface for the three types of polymer fibers studied.
Using SEM/EDX analysis, it is shown that the C/S ratios in the
PVA and C-S-H and nylon-6 and C-S-H interfaces are higher than
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that in the polypropylene and C-S-H interface. This is mainly a
result of the high polarity of the hydroxyl and amide functional
groups. To further investigate this observation, atomistic simula-
tions are performed to study the structure of C-S-H in the vicinity
of the three different polymers. The adhesion energies between the
polymers and the relevant C-S-H model were also found to study
the strength of polymer cement interfaces. Additionally, split-cyl-
inder testing was performed on samples and a correlation between
the polarity of the polymers’ functional groups (adhesion energies)
and load-displacement curves were found. This result was used
to investigate the macroscopic behavior of samples and was com-
pared to the molecular interaction between C-S-H and polymers.
The properties of the interface between fibers and cement paste
can be correlated with the fiber detachment in load-displacement
curves. The implications of these results are significant in further
development of robust fiber-reinforced cement composites.
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