Construction and Building Materials 228 (2019) 116749

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Composites reinforced with Guadua fibers: Physical and mechanical

properties
Martha L. Sánchez a,⇑, G. Capote b, J. Carrillo a
a
Department of Civil Engineering, Universidad Militar Nueva Granada, UMNG, Carrera 11 # 101-80, Bogotá D.C., Colombia
b
Faculty of Science, Department of Physics, Universidad Nacional de Colombia, Carrera 45 # 26-85, Bogotá D.C., Colombia

h i g h l i g h t s

Surface treatments increases the crystallinity and roughness of the fibers.

Surface treatments reduces the absorption capacity of fibers.

Panels elaborated with unidirectional fibers and plasma treatment presented higher values of strength and stiffness.

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

Article history: The need to mitigate the environmental impact produced by the use of conventional materials in the
Received 3 February 2019 construction sector of industry has motivated research based on alternative composite materials
Received in revised form 3 July 2019 reinforced with vegetable fibers. In this paper, the influence of the orientation of the fibers and the effect
Accepted 16 August 2019
of their surface treatments on the physical and mechanical properties of panels constructed using non-
Available online 23 August 2019
conventional materials were analyzed. For the manufacture of the composites, bamboo fibers and castor
oil resin were used. In order to evaluate the effect of the orientation of the fibers on the performance of
Keywords:
the composite, two fiber typologies were employed: long, unidirectional fibers and randomly-distributed
Composite panels
Vegetal fibers
short fibers. To modify the surface of the fibers, two methods were applied: a cold plasma treatment and
Orientation an alkaline treatment. The physical characterization was focused on the determination of the theoretical
Surface modifications and experimental density, the effective absorption, and the percentage of swelling. The mechanical char-
Physical properties acterization focused on the determination of the tensile, compression, and flexural behavior. In order to
Mechanical properties evaluate the degradation of the material with the temperature, a thermogravimetric test was performed.
The results obtained demonstrate the influence of the orientation and surface modifications of the fibers
on the physical and mechanical behavior of non-conventional composites.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction the use of petrochemical products has motivated the use of

The study of new materials called ‘‘bio-composites” has
increased significantly in various branches of modern industry,
mainly in civil engineering [1]. Composites made from the combi-
nation of fibers and resin of vegetal origin exhibit good mechanical
properties and low levels of toxicity, and they are biodegradable
and can be recycled, which contributes to reducing the environ-
mental impact generated by traditional materials [2]. Particularly
in the case of developing countries, the use of renewable sources
and resources has a favorable impact not only on the environment
but also on the economy and society [3]. According to Hu [4], the
increase in the economic and environmental crisis generated by
⇑ Corresponding author.
E-mail address: martha.sanchez@unimilitar.edu.co (M.L. Sánchez).
lignocellulosic materials as raw material for the manufacture of
biocompatible materials. On other hand, fossil fuel depletion and
other environmental effects associated with the production of
synthetic fibers have stimulated the search for new alternatives
using natural fibers [5]. It is for this reason that wood, hemp, jute,
sisal, and other vegetable fibers have emerged as reinforcement for
compounds made with a polymer matrix [6].
One application of vegetal fibers is their use in cementitious
composites, which is an innovative technical solution, but they
are characterized by a complex microstructure and significant
heterogeneity, which influence their interaction with cementitious
matrices [7]. It is for this reason that recently some articles have
focused on the study of plant matrices reinforced with vegetable
fibers. Torkaman et al. [8] presented a parametric study that eval-
uates the effects of the partial replacement of Portland cement

https://doi.org/10.1016/j.conbuildmat.2019.116749
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749
with wood fiber waste, rice husk ash, and limestone powder waste
for producing a lightweight concrete block as a building material.
In other experimental studies, Usman et al. [9] analyzed the feasi-
bility of the development of eco-friendly self-compacting cementi-
tious systems, utilizing waste sawdust for sustainable building
construction [9], while Xu et al. [10] used fibers produced from
wood waste to reduce the negative impact on the environment
and improve the mechanical properties of autoclaved aerated con-
crete [10].
According to Chaowana and Barbu [11], some bamboo species
have received special attention for different applications, princi-
pally as raw material for biocomposite materials such as fiber-
board, particleboard, and oriented strand board [11]. Due to their
wide availability, rapid growth, and mechanical properties, bam-
boo fibers of the Guadua Angustifolia Kunt species have found
application as reinforcement for polymer matrices [12].
For the use of vegetable fibers as reinforcement for polymeric
composites, it is necessary to take into consideration that most
of them are less dense than the synthetic fibers traditionally used
in manufactured composites [13]. This property, together with
their mechanical characteristics, makes this reinforcement a viable
option from an economic and technical point of view, mainly for
those applications in which the use of light, resistant, and durable
materials is required. Independent of the part of the plant (stem,
leaves, seeds, fruits, etc.), the properties of the fibers may vary con-
siderably [14]. It is for this reason that the selection of the fiber
type suitable for a given application depends not only on its origin
but also on parameters such as the diameter/length ratio, the
degree of polymerization, and the crystalline structure [15–18].
Several methods allow extraction of fibers from the stems of a
plant [13]. Mechanical extraction methods stand out for their
speed, simplicity, and economy. However, it is important to con-
sider that depending on the origin of the fiber, surface degradation
can occur, which may affect its performance as a reinforcement of
the composite. On the other hand, fibers obtained by mechanical
means are generally thicker than fibers obtained with biological,
physical, or chemical methods, which affects their diameter/length
ratio [13].
Recent studies have shown that the surface texture of the fibers
affects the mechanical performance of bio-composites. Through
the application of techniques such as scanning electron microscopy
(SEM) and atomic force microscopy (AFM), it has been possible to
verify that the roughness of the fibers is a factor that favorably
influences the adhesion between the fibers and the resin used as
a matrix [19]. The presence of wax substances on the surface of
the fibers prevents adequate impregnation of the resin, which
leads to the development of a weak and poorly-bonded interface
[20].
Research results have shown that with the application of some
chemical treatments it is possible to improve the performance of
nanomaterials for use in cement composites. In Lu et al. [21,22],
they used the modified hummer method for preparing a graphene
oxide for use as reinforcement in cement-based materials [21,22].
On the other hand, it has been found that with the application of
physical or chemical modification methods on the surface of the
fibers, it is possible to increase their roughness [23–26]. Physical
methods change the structural and surface properties of the fiber
and affect the mechanical bonding between the fiber and the
matrix. Two physical methods usually used for the surface modifi-
cation of fibers are corona treatment and plasma treatment.
According Faruk et al. [27], corona treatment is one of the most
important techniques for surface oxidation activation. The use of
this technique on cellulose fibers and hydrophobic matrices was
found to be effective for the improvement of the compatibilization
between hydrophilic fibers and a hydrophobic matrix [27].
One of the most-used physical methods for modifying the sur-
face of the material is the plasma treatment. Plasma is an ionized
gas that contains positive, negative, and neutral particles. When
a material is exposed to a gas, the charged particles are able to
chemically interact, modifying their surface [27]. Recent studies
have shown that regardless of the type of plasma used (argon,
methane, etc.) and the duration and specific conditions of the
treatment, it is possible to modify not only the roughness of the
fibers but also their hydrophobicity [27–30]. Sinha and Panagrahi
[28] studied the influence of plasma treatment on the morphology,
wettability, and structure of fibers and its impact on the interfacial
adhesion of natural fiber-reinforced thermosets [28]. For this
investigation, jute fibers were treated with argon cold plasma at
different periods of exposure and processed for a composite using
an unsaturated polyester resin. In others investigations, Scacili
et al. [29] showed the effect of plasma treatment on the properties
of natural fibers extracted from the leaf of the giant reed Arundo
Donax L. and their compatibility with a bio-based epoxy resin
[29], while Li et al. [30] used an atmospheric helium plasma treat-
ment in order to reveal the degree of improvement in the mechan-
ical properties of ramie fabric-reinforced polypropylene
composites [30].
Chemical modifications of natural fibers aimed at improving the
adhesion within the polymer matrix using different chemicals have
been extensively investigated. One of the most frequently used
chemical methods for fiber surface modification is treatment with
sodium hydroxide solution. Recent results show that by subjecting
a volume of fibers to an alkaline solution for a given period, it is
possible to modify its crystallinity and partially remove the lignin
and hemicellulose and other substances from the fibers. The appli-
cation of this type of treatment causes modifications in the hydro-
xyl groups present in the amorphous regions of the material,
improving its reaction with the binder. However, high solution
concentrations or excessive treatment times can significantly dete-
riorate the fibers, resulting in loss of strength and stiffness [31–36].
Other methods for the surface modification of natural fibers are
acetylation and silane treatments. The acetylation method consists
of the introduction of an acetyl functional group into an organic
compound. The purpose of this method is to coat the OH groups
of the fibers, which are responsible for their hydrophilic character,
with molecules that have a more hydrophobic nature [27,33]. The
surface energy of the fibers is related to their hydrophilic nature.
Silane coupling agents may contribute hydrophilic properties to
the interface, principally when amino-functional silanes such as
epoxies and urethane silanes are used as primers for reactive poly-
mers [27].
In addition to the type of fiber and its composition, factors such
as sides, length, and aspect ratio (length/diameter) exert a large
influence on the processing of polymeric composites as well as
their mechanical performance [27]. Recently, several studies have
focused on the study of the effect of fiber orientation on the perfor-
mance of biocomposites [37,38]. Kumar et al. [37] evaluated the
effect of fiber orientation on the tensile behavior of biocomposites
prepared from nettle and poly(lactic acid) fibers [37]. Mancino
et al. [38] evaluated the behavior of biocomposites obtained using
random short fibers, discontinuous short fibers, and long unidirec-
tional fibers as reinforcements for the composites [38].
1.1. Significance of this investigation
Interest in the preservation of the environment has now
motivated researchers to formulate new alternatives to replace
petroleum products that are currently used as resins. Therefore,
it is important to develop new plant polymers obtained from the
processing of oils extracted from the seeds of some plants. In spite
 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749
of advances in the study of compounds reinforced with vegetal
fibers, at the moment there is a lack of sufficient information about
the mechanical performance of compounds made with fibers and
vegetable resin.
In the present paper, a composite made up of Guadua fibers and
castor oil-based resin is studied. The influence of the orientation of
the fibers and the effect of their surface treatment on the physical
and mechanical properties of biocomposite panels is presented. In
order to analyze the effect of the orientation of the fibers, two con-
ditions were considered: randomly-distributed short bamboo
fibers and unidirectional long bamboo fibers. For the construction
of composites made with randomly-distributed fibers, short fibers
of 15 mm in length were used. For unidirectional composites,
fibers of 300 mm were used as reinforcement. For surface modifi-
cation, plasma and alkaline treatments were applied. Evaluation
of the physical and mechanical properties of the panels was carried
out through laboratory tests of percentage of swelling, density,
effective absorption, tensile, compression, and static bending.
Thermal degradation was evaluated by means of the thermogravi-
metric analysis of the composite panels.
2. Materials and methods
2.1. Constituent materials
For the manufacturing process, fibers extracted the top of Gua-
dua angustifolia Kunth bamboo culms were used. The average age
of the Guadua culms was three years old. Guadua preservation is
considered to be a requirement for guaranteeing the durability of
the material. It is for this reason that all the culms used for the
extraction of the fibers were immunized by immersion in borax
and boric acid salts at a concentration of 3% [39]. A castor oil-
based resin was used as an adhesive. This resin consists of the com-
bination of two vegetable components: an isocyanate and a poliol-
polyester, mixed at a 1:1.5 ratio, according to the recommenda-
tions of the provider.
2.2. Separation of fibers
According to Bavan and Kumar [40], the separation process is an
important step toward obtaining high-quality fibers. For this pur-
pose, a mechanical crusher was used. Before the extraction process,
the culms were submerged in a water tank for a period of three
days. Bundles of fibers 50 cm long were obtained and later cut to
the required lengths (15 mm and 300 mm).
2.3. Surface modification
For the surface modification, two procedures were employed:
an alkaline treatment and a plasma treatment. For the chemical
treatment, constant conditions were established based on the liter-
ature reviewed [33–36]. The treatment consisted of the immersion
of the crushed material in a 5% sodium hydroxide solution for a
period of 48 h at room temperature. This process was followed
by washing with distilled water and a drying process until reaching
a constant mass value.
For the plasma treatment, untreated fibers were subjected to
the uniform action of a methane cold plasma for 10 min using a
working pressure of about 27 Pa and a DC potential of 700 V, with
a gas flow of 10 sccm and temperature between 18 °C and 26 °C.
Treatment conditions were established based on the literature
reviewed [28–30]. This method can be considered a clean process
capable of modifying the surface of the fibers without affecting
the bulk properties, and it generates fewer pollutants than conven-
tional chemical treatment [41,42].
3
2.4. Fourier transform infrared spectroscopy (FTIR)
For the determination of the characteristic absorption bands of
the most common functional groups in the bamboo fiber, the Four-
ier transform infrared (FTIR) spectroscopy technique was
employed. The use of this technique allows evaluating the partial
removal of lignin in the fibers by detecting the typical functional
groups of this polysaccharide and its typical absorption bands.
The spectra were obtained with a resolution of 4 cm1, within a
spectral range of 500–4000 cm1 with 32 sweeps. The spectra were
processed with Omnic 9.1 software.
2.5. X-ray diffraction
X-ray diffraction (XRD) analysis was carried out using a PANa-
lytical XPert PRO MRD X-ray diffraction system. The equipment
uses a copper anode tube (k = 1.54060 Å), a standard resolution
goniometer containing the geometry (0h–2h) for performing mea-
surements, symmetrical and asymmetrical configurations, a mini-
mum step size of 0.002°, and an X-ray proportional counter. The
crystallinity index (Ic) was calculated using Eq. (1): [43]
ðIca  Ia Þ
IC ¼ 100 ð1Þ
Ic
where IC is the crystallinity index in %, Ica is the maximum intensity
of diffraction at an angle of 2h between 22° and 23°, and Ia is the
intensity of the diffraction in angle of 2h between 25° and 27°
where the intensity is minimum.
2.6. Topography of the fibers
In order to evaluate surface variations in the topography of the
fibers, untreated and treated fibers were observed. For this pur-
pose, the roughness of the fibers was studied via atomic force
microscopy (AFM) (Nanosurf Atomic force microscope) on an area
of 50  50 mm. The average roughness was calculated using the
average height of the irregularities observed in the direction per-
pendicular to the surface of fifty samples for each type of
treatment.
2.7. Evaluation of the physical properties of the fibers
For the determination of the physical properties of the fibers,
five groups of fibers were prepared in an untreated condition, with
chemical treatment, and with plasma treatment. Each group con-
sisted of 10 fiber bundles composed of five fibers of 5 cm in length.
The evaluation of the moisture content, the absorption percentage,
and the relative density of the fibers was carried out according to
the specifications of the standards ASTM D 4442-16 [44], ASTM
D5229-14 [45], and ASTM D3800-16 [46].
2.8. Manufacture of the panels
The dosing of the constituent materials was done with a steel
mold of 300  300 mm with an average thickness of 6 mm. In
order to establish the mixing proportions of the adhesive, at the
suggestion of the supplier the use of a 1:1.5 ratio (isocyanate:
polyol polyester) was selected. The use of these proportions allows
a workability period of approximately 20 min before starting the
drying process. For the selection of the volumetric fraction of the
fibers, a compaction test was previously carried out. The variation
of the thickness of the panels with the value of the applied com-
pression load was evaluated, thus determining the fiber volume
for each test condition. The results of the pre-compaction test
showed that it is necessary to use a fiber volume of 70% for panels
of a thickness of about 7 mm. For this reason, the constituent mate-
4 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749

rials were mixed in a proportion of 70% fibers/30% resin with 120

respect to the total volume of the panel. In order to develop a uni- Untreated
100
directional long fiber reinforcement, ‘‘manually sewn” unidirec-
tional fabrics were developed, straightening and aligning the 80
fibers prior to their placement in the composite. 60
The manufacture of the panels was carried out using the com- 40
pression molding at room temperature [47]. This method consists
20
of placing successive layers of fibers on a mold, doing the manual
impregnation of the resin, and compacting each layer in order to 120
0
Sodium hidroxide

Transmittance (%)
eliminate the air bubbles and at the same time contribute to the 100
homogeneous distribution of the fibers and the resin in the mold. 80
For the compression, a hydraulic press was used. The compression
load was 18 tons, and the compaction time was 18 h. Once 60
removed from the mold, the panels were cured for 96 h at room 40
temperature. 20
120
0
2.9. Evaluation of the physical and mechanical properties of the panels Plasma
100
The physical characterization of the composite was based on 80
the determination of its theoretical and experimental density, 60
effective absorption at 2 h and 24 h, and percentage of swelling 40
at 2 h and 24 h. The experimental density was calculated according
the specifications of ASTM D-2395 [48]. To estimate the percentage 20
of effective absorption, the methodology described in ASTM D4442 0
[44] was employed. The percentage of swelling was calculated 4000 3500 3000 2500 2000 1500 1000 500
-1
from the variation of thickness of square specimens of 50 mm in Wavenumber (cm )
width after being submerged in water for periods of 2 h and 24 h.
Fig. 1. Characteristic absorption bands.
The evaluation of the mechanical properties consisted of carry-
ing out tensile, compression, and static bending tests. For these
tests, the specifications of ASTM 1037-12 were applied [49]. The
Table 1
mechanical characterization was performed on an MTS Landmark Peak absorption bands (in cm1).
370.10, using an operating range of up to 100 kN.
Bands Untreated Alkaline Plasma
treatment treatment
2.10. Thermogravimetric analysis
OAH stretching 3422.77 3386.45 3405.24
CAH stretching (aliphatic 2919.12 2924.63 2922.27
The experimental parameters of the TGA analysis were deter- + aromatic)
mined in an inert nitrogen atmosphere with a flow of 100 mL/ C@O stretching (carboxylic 1685.93 1751.71 1749.05
groups)
min using a TA Instruments SDT-Q600. The characterization was
C@O stretching in conjugation to 1654.95 1654.82 1637.99
performed on specimens of 6–10 mg from room temperature to aromatic ring
700 °C with a heating rate of 10 °C/min. The specimens were pul- Aromatic ring vibrations 1627.78 1595.13 1509.18
verized by the use of a metal file and a fine grater. CAH deformations 1459.10 1459.76 1459.06
Aromatic ring vibrations 1421.18 1411.68 1422.88
CAC, CAO stretch 1245.85 1202.84 1245.87
3. Results and discussion CAO stretching of conjugated 1157.67 1159.34 1156.81
ester groups
CAH, CAO deformations 1079.62 1034.89 1079.55
This section presents and discusses the influence of the orienta-
CAH out of plane in p- 1022.45 900.81 577.36
tion of the fibers and the surface modification on the physical and hydroxyphenyl units
mechanical properties of panels made using non-conventional
materials.
hemicellulose present in alkaline treated fibers. A peak at
3.1. Fourier transform infrared spectroscopy (FTIR) 1245 cm1 was identified in untreated and plasma-treated fibers,
indicating the presence of this polysaccharide. Other absorption
The characteristic absorption bands of Guadua fibers were ana- bands can be observed between 1150 and 900 cm1 wavenumber.
lyzed via Fourier transform infrared spectroscopy (FTIR). Spectras Similar absorption bands were reported by Usman et al. [9] for
for untreated and treated fibers were obtained. The results are wood waste, and they can be associated with typical structures
shown in Fig. 1. The peaks of the absorption bands are summarized of cellulose compounds [9].
in Table 1. From the results shown in Fig. 1, it is possible to observe that
From the results presented in Table 1 it is possible to distin- the treated and untreated fibers exhibit similar spectra. However,
guish absorption bands close to 1650 and 1750 cm1, which indi- a comparative analysis of the spectra allows verifying the effect
cate the existence of free and esterified carboxylic groups of the surface modification of the fibers. The increase in absorption
characteristic of pectin present in the fiber. Functional groups typ- in the regions close to 3405.24 cm1, 2922.27 cm1, 1637.99 cm1,
ical of cellulose are visible in the absorption bands 3405.24, 1374.59 cm1, and 1023.35 cm1 could be associated with a
2922.27, 1637.99, 1374.59, and 1023.35 cm1. Functional groups greater stretching of the characteristic bonds of the cellulose struc-
associated with characteristic bands close to 1459 cm1 can indi- ture. On the other hand, the decrease in absorption in the region
cate the presence of hemicellulose in all types of fibers. A peak in nearest 1751 cm1 can be attributed to the partial removal of lig-
the absorption band close to 1382 cm1 could be associated with nin and hemicelluloses.
 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749
3.2. X-ray diffraction
The crystallinity of the fibers was evaluated using X-ray diffrac-
tion. Diffractograms of treated and untreated Guadua fibers are
shown in Fig. 2. The graph shows the presence of two characteristic
peaks of a cellulose molecule: one peak of greater intensity at 24°
and another less acute at 27°. The measurement of the crystallinity
index is shown in Table 2.
The results shown in Table 2 indicate that with the application
of the treatment on the surface of the fibers it is possible to
increase their crystallinity by up to 10%. On comparing the results
of the crystallinity index obtained after the alkaline treatment and
the plasma treatment, a difference of less than 5% was observed
between the treatments. The values obtained are in agreement
with those presented by Kammatova [50] and Sair et al. [51]. These
results suggested that the treatments contribute to removing the
non-crystalline compounds from the fiber, increasing the percent-
age of cellulose. According to Ansari [52], the increase in the crys-
tallinity of the fibers can cause a reduction in their absorption
capacity and a decrease in the percentage of swelling of panels
made with this type of fiber, affecting the performance of the
material during its service life.
3.3. Topography and physical properties of Guadua fibers
The roughness and the physical properties of the fiber bundles
were determined using the procedures described in Sections 2.6
and 2.7. AFM images are showed in Fig. 3. The physical properties
are shown in Table 3.
From the results shown in Table 3 it is possible to note an
increase in the roughness of the fibers after the modification of
their surface. These modifications in the topography of the fibers
are similar to those presented by Oushabi et al. [53] and make it
possible to verify that when performing a treatment with 5%
sodium hydroxide it is possible to partially eliminate lignin, waxes,
oils, and other impurities that remain adhered to the fibers during
the separation process. The cleaning of the surface of the fibers and
100000
80000
60000
40000
20000
100000
Sodium hidroxide
Intensity (a.u)
80000
60000
40000
20000
100000
80000
60000
40000
20000
10 15 20
2Θ
Fig. 2. X-ray diffractograms for Guadua fibers.
5
Table 2
Index of crystallinity of Guadua fibers.
Untreated Plasma treatment Alkaline treatment
IC (%) 65.9 72.4 69.2
therefore a better definition of the microfibers that compose it
allow an increase in the roughness of the material, which con-
tributes to increasing its adherence to the resin used as matrix of
the composite. Similar results were observed when analyzing the
fibers treated with methane cold plasma. Independently of the
type of treatment, the partial dissolution of compounds such as lig-
nin and hemicellulose during the treatment causes a loss of mass
of the fibers, generating a decrease in the value of their relative
density. However, a greater loss of mass was observed in fibers
treated with plasma.
Another important factor is the effect of the modification of the
surface of the fibers on their absorption capacity. Lignocellulosic
fibers possess free hydroxyl groups that attract water molecules
[54]. Recent studies have shown that the reduction of the mechan-
ical strength of panels made with materials of vegetal origin can be
partially attributed to the water absorbed by the fibers that act as
reinforcement [55]. The results shown in Table 3 indicate that on
performing an alkaline treatment it is possible to reduce the
absorption capacity of Guadua fibers by approximately 30%. For
fibers treated with plasma, this reduction can reach approximately
60%. On treating the fibers with cold methane plasma, a very thin
layer of hydrogenated amorphous carbon is generated on the sur-
face of the material, which contributes to reducing its absorption
capacity.
3.4. Physical and mechanical properties of Guadua panels
To evaluate the effect of the orientation of the fibers and the
type of treatment on the properties of the panels, the nomencla-
ture described in Table 4 was established. The determination of
the physical properties of Guadua panels was developed according
to the procedures described in Section 2.9. The physical character-
ization was based on the determination of the theoretical (TD) and
experimental density (ED), effective absorption (A), and percentage
Untreated
of swelling (H) at 2 h and 24 h. The results are shown in Table 5.
The experimental density was calculated using Eq. (2):
ED ¼ Df V f þ Dm Dm ð2Þ
where ED is the density of panel in g/cm3, Df is the density of Gua-
dua fiber in g/cm3, Dm is the density of vegetal resin in g/cm3, and Vf
and, Vm are the volumetric fractions of fibers and resin in the com-
posite, respectively.
Results shown in Table 5 demonstrate the effect of the type of
treatment on the effective absorption of panels made with unidi-
rectional fibers. For instance, it is evident in the table a reduction
of 26% in the absorption values for the GUP panels with respect
to the values obtained for fibers treated with alkaline solution
(GUM panels). Similar results can be observed for the percentage
Lg
of swelling values. However, the increase in density is approxi-
mately 10%. The results obtained affect not only the dosage of
the fibers to be used in the elaboration of the panels, but also their
weight and durability. The increased hydrophobicity of the fibers
favors the development of a suitable fiber-matrix bond, contributes
to the dimensional stability of the composite, and improves their
performance, mainly in those applications in which they are
25 30 exposed to wet conditions for long periods. Panels made with uni-
directional fibers exhibited higher density, dimensional stability,
and lower absorption capacity. Panels made with unidirectional
fibers treated with plasma showed an increase of close to 20% in
6 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749

Untreated Alkaline treatment Plasma treatment

Fig. 3. AFM images.

Table 3
Physical properties of vegetal fibers. The evaluation of the mechanical properties of the panels was
performed according to the procedures described in Section 2.9.
Properties Untreated Akaline treatment Plasma treatment
The results are shown in Table 6.
Moisture content (%) 8 ± 0.9 9 ± 0.4 9 ± 1.40 The results shown in Table 6 indicate that the values of the
Absorption (%) 63 ± 1.3 45 ± 2.4 28 ± 6.05
rupture modulus and the flexural modulus were affected by the
Density (g/cm3) 0.8 ± 0.04 0.7 ± 0.2 0.6 ± 0.03
Roughness (mm) 804 1723 2275 orientation of the fibers and their surface modification process.
The rupture modulus of the GUP panels exhibited the highest prop-
erties of (165.4 MPa), which are almost 6% greater than the
Table 4 strength of the GUM panels, and about 65% greater than that of
Nomenclature of panels. the GRP panels. Static bending tests showed that the treatment
also affect significantly the flexural modulus. The GUP panels
Nomenclature Description
exhibited the greatest improvement in terms of their stiffness,
GUP Panels elaborated with unidirectional fibers and plasma
which is an indicator of better adhesion between the constituent
treatment
GUM Panels elaborated with unidirectional fibers and alkaline
materials (fibers and matrix).
treatment Results shown in Table 6 also indicate that the tensile stress of
GRP Panels elaborate with randomly fibers and plasma treatment the GUP panels is approximately 11% higher than the values
GRM Panels elaborated with randomly fibers and alkaline obtained for the GUM panels, and about 90% greater than the
treatment
results obtained for the GRP and GRM panels. These increments
show the effect of the orientation of the fibers on the behavior of
the composite when is subjected to axial loads. In terms of the
the value of the density and a reduction of approximately 37% in Young modulus, an increase of 90% in the stiffness of the composite
the absorption capacity when compared with panels made with for panels with unidirectional fibers is observed in Table 6. A
randomly-distributed fibers. Similar results were found in panels reduction of nearly 30% in the Young modulus was observed in
made with fibers treated with sodium hydroxide, demonstrating panels made with fibers treated with alkaline solution. When com-
the effect of fiber distribution on the physical properties of the paring the results obtained in the compression tests, a maximum
material. These results allow verifying that the orientation and dis- variation of 60% in the compressive stress value is observed for
tribution of the fibers affect the porosity of the panels, contributing panels made with different fiber types. The modification of fibers
to the low permeability of this type of material. with plasma treatment causes an increase of approximately 30%

Table 5
Physical properties of panels.

Panel D.E (g/cm3) D.T (g/cm3) H 2 h (%) H 24 h (%) A (%) 2 h A (%) 24 h

GUP 1.10 ± 0.04 1.06 ± 0.05 4.50 ± 0.03 7.50 ± 0.04 6.80 ± 0.05 11.60 ± 0.06
GUM 0.93 ± 0.06 0.96 ± 0.07 6.40 ± 0.05 10.50 ± 0.06 9.90 ± 0.04 15.70 ± 0.08
GRP 0.86 ± 0.04 0.90 ± 0.03 8.40 ± 0.05 20.15 ± 0.07 12.70 ± 0.03 18.50 ± 0.04
GRM 0.78 ± 0.05 0.83 ± 0.04 10.80 ± 0.07 25.00 ± 0.06 18.20 ± 0.05 23.60 ± 0.06

Table 6
Mechanical properties of panels.

Mechanical properties (MPa) GUP GUM GRP GRM

Compression Maximum stress 56 ± 6.3 38 ± 5.9 22 ± 6.3 18 ± 6.7
Young modulus 6439 ± 35 3517 ± 27 2653 ± 65 2350 ± 53
Bending Rupture modulus 165.4 ± 8.3 155.2 ± 7.1 55.0 ± 5.9 37.0 ± 4.6
Flexural modulus 14820 ± 420 10170 ± 223 4800 ± 47 3700 ± 31
Tensile Maximum Stress 203 ± 6.1 180 ± 8.9 15 ± 6.3 11 ± 6.3
Young Modulus 15929 ± 460 11167 ± 180 1300 ± 41 2600 ± 82
 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749
Fig. 4. Thermogravimetry results for GUM panels.
Fig. 5. Thermogravimetry results for GUP panels.
in the values of maximum stress and Young modulus. Fibers trea-
ted with methane cold plasma exhibited improved physical prop-
erties, which caused an increase in both the mechanical strength
and the stiffness of the panels. At the same time, plasma treatment
increases the hydrophobicity of the fibers, which improves the per-
formance of the material when subjected to wet conditions.
3.5. Thermo gravimetric analysis
A thermogravimetric analysis was performed for panels made
with unidirectional fibers to analyze the effect of the treatments
on the degradation of the panels with the temperature. The results
are shown in Figs. 4 and 5.
Several stages of decomposition can be observed in Figs. 4
and 5. In stage 1, mass losses at temperatures below 100 °C
can be attributed to the moisture loss of the composite. In stage
2, mass losses between 100 °C and 200 °C can be associated with
the decomposition of the hemicellulose present in the fibers that
act as reinforcement. In stage 3, mass losses between 200 °C and
415 °C can be associated with the decomposition of vegetal poly-
urethane. In stage 4, mass losses between 360 °C and 420 °C can
be associated to the decomposition of the cellulose. These results
are consistent with those found in previous research, which
show that the degradation of lignocellulosic materials can be
divided into four stages: moisture loss, decomposition of hemi-
cellulose, cellulose decomposition and lignin decomposition
[53]. The difference in the thermal stability of hemicellulose
and cellulose can be attributed to the differences in their chem-
ical composition. Hemicellulose is composed of several random
7
and amorphous structures, which are easy to remove at low
temperatures, while cellulose is formed by a polymer of glucose
without branches, and the thermal stability of cellulose is higher.
As for the decomposition of lignin, its degradation occurs over a
wide range of temperatures between 100 °C and 900 °C. How-
ever, the lignin of the Guadua fibers was removed during the
surface treatments. It is for this reason that the degradation
peaks associated with this compound were not observed. On
other hand, degradation of castor oil-based resin was detected
between 200 °C and 415 °C. From the thermogravimetric analysis
it can be established that the vegetable resin is thermally stable
below 200 °C. Similar results were obtained by Yang et al. [56].
The degradation of polyurethane could be related to the mois-
ture loss of the linear aliphatic hydrocarbons of the castor oil.
This process is followed by the volatilization of the branches
present in the molecules that form urethane bonds, which leads
to the decomposition of the polyurethane branch. The tempera-
ture ranges observed in this analysis are different from those
analyzed by Hanif et al. [57] for the analysis of the thermal
decomposition of cement compounds, in which a decarbonation
of CaCO3 at around 650 °C was observed [57].
4. Conclusions
The effect of the orientation of the fibers and the influence of
surface treatments on the behavior of panels made with Guadua
fibers and a castor oil-based resin was evaluated.
The experimental results prove that the crystallinity index and
the average roughness increase when a treatment is applied on the
surface of the vegetal fibers. These modifications contribute to
reducing the absorption capacity and the percentage of swelling
of biocomposite panels, thus improving the performance of the
composite during its service life.
Results of physical characterization confirmed the influence of
the orientation of the fibers on the properties of biocomposites.
Panels made with unidirectional fibers exhibited higher density
values, greater dimensional stability, and lower absorption capac-
ity. The distribution of the fibers affects the porosity of the panels,
contributing to the low permeability of this type of material.
Results of mechanical tests demonstrated that the values of the
mechanical strength and the stiffness of the composite increase
when performing a plasma treatment, mainly when the material
is subjected to axial loads (tensile, compression). However, other
factors, such as the percentages of the mixture and the method
of molding and compaction, affect the performance of the material
and should be analyzed in future investigations.
Despite progress in the study of biocomposites, some studies,
among which is the analysis of adhesion in the fiber-matrix inter-
face through pull-out tests, are recommended as future research.
Another important recommendation is the construction of numer-
ical models that allow predicting the mechanical performance of
the material from the elastic properties of the constituent
materials.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
Acknowledgment
This paper is a derivative product of the project INV-ING-2623
financed by the Vicerectory of Research of Universidad Militar
Nueva Granada-validity (2018).
8 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749

References [26] H.P.S. Abdul Khalil, I.U.H. Bhat, M. Jawaid, A. Zaidon, D. Hermawan, Y.S. Hadi,
Bamboo fibre reinforced biocomposites: a review, Mater. Des. 94 (2012) 180–
192, https://doi.org/10.1016/j.matdes.2012.06.015.
[1] M. Ramesh, K. Palanikumar, K.H. Reddy, Mechanical property evaluation of
[27] J. Fiorelli, F.A.R. Lahar, M.F. do Nascimento, H. Savastano, J.A. Rossignolo,
sisal– jute–glass fibre reinforced polyester composites, Compos. Part B. 48
Painéis de partículas à base de bagaço de cana e resina de mamona – produção
(2013) 1–9, https://doi.org/10.1016/j.compositesb.2012.12.004.
e propriedades, Acta Sci. Technol. 33 (4) (2011) 401–406, https://doi.org/
[2] D. Ray, S. Sengupta, S.P. Sengupta, A.K. Mohanty, M. Misra, A study of the
10.4025/actascitechnol.v33i4.9615.
mechanical and fracture behaviour of jute–fabric–reinforced clay-modified
[28] O. Faruk, A.K. Bledzki, H. Fink, M. Sain, Biocomposites reinforced with natural
thermoplastic starch-matrix composites, Macromol. Mater. Eng. 292 (2007)
fibers: 2000–2010, Prog. Polym. Sci. 37 (2012) 552–1596, https://doi.org/
1075–1084, https://doi.org/10.1002/mame.200700111.
10.1016/j.progpolymsci.2012.04.003.
[3] K.G. Satyanarayana, J.L. Guimarães, F. Wypych, Studies on lignocellulosic fibers
[29] E. Sinha, S. Panigrahi, Effect of plasma treatment on structure, wettability of
of Brazil. Part I: source, production, morphology, properties and applications,
jute fiber and flexural strength of its composite, J. Compos. Mater. 43 (17)
Compos. A 38 (7) (2007) 1694–1709, https://doi.org/10.1016/
(2009) 1791–1802, https://doi.org/10.1177/0021998309338078.
j.compositesa.2007.02.006.
[30] T. Scalici, V. Fiore, A. Valenza, Effect of plasma treatment on the properties of
[4] T.Q. Hu, Characterization of Lignocellulosic Materials, Wiley-Blackwell, 2008.
Arundo Donax L. leaf fibres and its bio-based epoxy composites: a preliminary
ISBN: 978-1-4051-5880-0.
study, Compos. B Eng. 94 (2016) 167–175, https://doi.org/10.1016/
[5] A. Pietak, S. Korte, E. Tan, A. Downard, M.P. Staiger, A novel technique for
j.compositesb.2016.03.053.
characterizing the surface of natural fibres, Appl. Surf. Sci. 253 (2007) 3627–3635.
[31] Y. Li, S. Moyo, Z. Ding, Z. Shan, Y. Qiu, Helium plasma treatment of ethanol-
[6] S. Leduc, J.R.G. Urena, R. Gonzalez-Nunez, J.R. Quirarte, B. Riedl, D. Rodriguez,
pretreated ramie fabrics for improving the mechanical properties of ramie/
LDPE/ Agave fibre composites: effect of coupling agent and weld line on
polypropylene composites, Ind. Crops Prod. 51 (2013) 299–305, https://doi.
mechanical and morphological properties, Polym. Polym. Compos. 16 (2008)
org/10.1016/j.indcrop.2013.09.028.
115–124.
[32] H. Gu, Tensile behaviors of the coir fibre and related composites after NaOH
[7] S.R. Ferreira, M. Pepe, E. Martinelli, F. de Andrade Silva, R.D. Toledo Filho,
treatment, Mater. Des. 30 (2009) 3931–3934, https://doi.org/10.1016/
Influence of natural fibers characteristics on the interface mechanics with
j.matdes.2009.01.035.
cement based matrices, Compos. B Eng. 140 (2018) 183–196, https://doi.org/
[33] B.L.S. Sipião, S.A.S. Goulart, T. Sousa, D.R. Mulinari, Analysis of mechanical
10.1016/j.compositesb.2017.12.016.
behavior of polymeric composites reinforced with palm fibers, Frontiers
[8] J. Torkaman, A. Ashori, A. Sadr, A. Sadr Momtazi, Using wood fiber waste, rice
Polymer Science, Elsevier, Lyon-France, 2011.
husk ash, and limestone powder waste as cement replacement materials for
[34] M. Rokbi, H. Osmani, A. Imad, N. Benseddiq, Effect of Chemical treatment on
lightweight concrete blocks, Constr. Build. Mater. 50 (2014) 432–436, https://
Flexure Properties of Natural Fiber-reinforced Polyester Composite, ICM11,
doi.org/10.1016/j.conbuildmat.2013.09.044.
2011.
[9] M. Usman, A.Y. Khan, S.H. Farooq, A. Hanif, S. Tang, R.A. Khushnood, S.A.
[35] A. Orue, A. Jauregi, U. Unsuain, J. Labidi, A. Eceiza, A. Arbelaiz, The effect of
Rizwan, Eco-friendly self-compacting cement pastes incorporating wood
alkaline and silane treatments on mechanical properties and breakage of sisal
waste as cement replacement: a feasibility study, J. Cleaner Prod. 190 (2018)
fibers and poly(lactic acid)/sisal fiber composites, Compos. Part A Appl. Sci.
679–688, https://doi.org/10.1016/j.jclepro.2018.04.186.
Manuf. 84 (2016) 186–195, https://doi.org/10.1016/
[10] R. Xu, T. He, Y. Da, Y. Liu, J. Li, C. Chen, Utilizing wood fiber produced with
j.compositesa.2016.01.021.
wood waste to reinforce autoclaved aerated concrete, Constr. Build. Mater. 208
[36] V. Fiore, G. Di Bella, A. Valenza, The effect of alkaline treatment on mechanical
(2019) 242–249, https://doi.org/10.1016/j.conbuildmat.2019.03.030.
properties of kenaf fibers and their epoxy composites, Compos. B Eng. 68
[11] P.Chaowana, M.C.Barbu, Bamboo: Potential material for biocomposites,
(2015) 14–21, https://doi.org/10.1016/j.compositesb.2014.08.025.
Lignocellulosic Fibre and Biomass-Based Composite Materials, Processing,
[37] D. Bachtiar, S.M. Sapuan, M.M. Hamdan, The effect of alkaline treatment on
Properties and Applications, Woodhead Publishing Series in Composites
tensile properties of sugar palm fibre reinforced epoxy composites, Mater. Des.
Science and Engineering, 2017, pp. 259–289. Doi: 10.1016/B978-0-08-
29 (2008) 1285–1290, https://doi.org/10.1016/j.matdes.2007.09.006.
100959-8.00013-5.
[38] K. Kumar, D. Das, B. Necká, Effect offiber orientation on tensile behavior of
[12] M. Espitia, C. Sjogreen, N. Rodríguez, J. Calderón, A. Benavides, R. Peraza, G.
biocomposites preparedfrom nettle and poly(lactic acid)fibers: modeling &
Espitia, R. Nemocon, Mechanical and physical characterization of Guadua
experiment, Compos. B 138 (2018) 113–121, https://doi.org/10.1016/
angustifolia ‘Kunth’ fibers from Colombia, Revista UIS Ingenierías 17 (2) (2018)
j.compositesb.2017.11.019.
33–40.
[39] A. Mancino, G. Marannano, B. Zuccarello, Implementation of eco-sustainable
[13] M. Misra, J.K. Pandey, A.K. Mohanty, Biocomposites: Design and Mechanical
biocomposites materials reinforced by optimized agave fibers, Proc. Struct.
Performance, first ed. ISBN 978-1-78242-373-7, 2015.
Integr. 8 (2018) 526–538, https://doi.org/10.1016/j.prostr.2017.12.052.
[14] R.B. Yusoff, H. Takagi, A.N. Nakagaito, Tensile and flexural properties of
[40] Norma Técnica Colombiana NTC 5301, Preservación y Secado del culmo de
polylactic acid-based hybrid green composites reinforced by kenaf, bamboo
Guadua Angustifolia Kunth, Editorial Icontec.
and coir fibers, Ind. Crops Prod. 94 (2016) 562–573, https://doi.org/10.1016/j.
[41] D.S. Bavan, G.C.M. Kuman, Conceptual design features and eco-methods, in:
indcrop.2016.09.017.
Amaresh Chakrabarti (Ed.), Research into Design — Supporting Sustainable
[15] N. Abilash, M. Sivapragash, Optimizing the delamination failure in bamboo
Product Development, Published by Research Publishing, Indian Institute of
fiber reinforced polyester composite, J. King Saud. Univ. Sci. 28 (1) (2016) 92–
Science, Bangalore, India, 2011.
102, https://doi.org/10.1016/j.jksues.2013.09.004.
[42] M.A. Lieberman, A.J. Lichtenberg, Principles of Plasma Discharges and
[16] M.M. Davoodi, S.M. Sapuan, D. Ahmad, A. Ali, A. Khalina, M. Jonoobi,
Materials Processing, second ed., John Wiley & Sons, Hoboken, NJ, 2005.
Mechanical properties of hybrid kenaf/glass reinforced epoxy composite for
[43] S. Nam, A.D. French, D.B. Condon, M. Concha, Segal crystallinity index revisited
passenger car bumper beam, Mater. Des. 31 (10) (2010) 4927–4932.
by the simulation of X-ray diffraction patterns of cotton cellulose Ib and
[17] K. Rassiah, M.M. Ahmad, A review on mechanical properties of bamboo fiber
cellulose II, Carbohydr. Polym. 135 (2016) 1–9, https://doi.org/10.1016/
reinforced polymer composite, Aust. J. Basic Appl. Sci. 7 (8) (2013) 247–253.
j.carbpol.2015.08.035.
[18] I.S. Aji, S.M. Sapuan, E.S. Zainudin, K. Abdan, Kenaf fibres as reinforcement for
[44] ASTM D 4442-16, Standard test method for direct moisture content
polymeric composites: a review, Int. J. Mech. Mater. Eng. 4 (3) (2009) 239–248.
measurement of wood and wood-based materials, Annual Book of ASTM
[19] M. Ramachandran, B. Sahas, R. Pramod, Experimental study of bamboo using
Standards, 2016.
banana and linen fiber reinforced polymeric composites, Perspect. Sci. 8 (2016)
[45] ASTM D5229-14, Standard test method for moisture absorption properties and
313–316, https://doi.org/10.1016/j.pisc.2016.04.063.
equilibrium conditioning of polymer matrix composite materials, Annual Book
[20] H.P.S. Abdul Khalil, M.S. Alwani, M.N. Islam, S.S. Suhaily, R. Dungani, Y.M. H’ng,
of ASTM Standards, 2014.
M. Jawaid, The use of bamboo fibers as reinforcements in composites, Biofiber
[46] ASTM D3800-16, Standard test method for density of high-modulus fibers,
Reinforce. Compos. Mater. (2015) 488–524, https://doi.org/10.1533/
Annual Book of ASTM Standards, 2016.
9781782421276.4.488.
[47] M.L. Sánchez, L.Y. Morales, J.D. Caicedo, Physical and mechanical properties of
[21] T. Yang, T. Wu, K. Hung, Y. Chen, J. Wu, Mechanical properties and extended
agglomerated panels made from bamboo fiber and vegetable resin, Constr.
creep behavior of bamboo fiber reinforced recycled poly (lactic acid) composites
Build. Mater. 156 (2017) 330–339, https://doi.org/10.1016/
using the time–temperature superposition principle, Constr. Build. Mater.
j.conbuildmat.2017.09.003.
(2015) 558–563, https://doi.org/10.1016/j.conbuildmat.2015.06.038.
[48] ASTM D-2395-14, Standard Test Methods for Density and Specific Gravity
[22] C. Lu, Z. Lu, Z. Li, C.K.Y. Leung, Effect of graphene oxide on the mechanical
(Relative Density) of Wood and Wood-Based Materials, Annual Book of ASTM
behavior of strain hardening cementitious composites, Const. Build. Mater.
Standards, 2014.
120 (2016) 457–464, https://doi.org/10.1016/j.conbuildmat.2016.05.122.
[49] ASTM D-1037-12, Standard Test Methods for Evaluating Properties of Wood-
[23] Z. Lu, A. Hanif, G. Sun, R. Liang, P. Parthasarathy, Z. Li, Highly dispersed
Base Fiber and Particle Panel Materials, Annual Book of ASTM Standards, 2012.
graphene oxide electrodeposited carbon fiber reinforced cement-based
[50] V.V. Khammatova, Effect of high-frequency capacitive discharge plasma on the
materials with enhanced mechanical properties, Cem. Concr. Compos. 87
structure and properties of flax and lavsan materials, Fibre Chem. 37 (4) (2005)
(2018) 220–228, https://doi.org/10.1016/j.cemconcomp.2018.01.006.
293–296.
[24] P. Zakikhani, R. Zahari, M.T.H. Sultan, D.L. Majid, Extraction and preparation of
[51] S. Sair, A. Oushabi, A. Kammouni, O. Tanane, Y. Abboud, F. Oudrhiri Hassani, A.
bamboo fiber-reinforced composites, Mater. Des. 63 (2014) 820–828, https://
Laachachi, A. El Bouari, Effect of surface modification on morphological,
doi.org/10.1016/j.matdes.2014.06.058.
mechanical and thermal conductivity of hemp fiber: characterization of the
[25] W.H. Negrão, S.A.M. da Silva, A.L. Christoforo, F.A.R. Lahr, Painéis aglomerados
interface of hemp –Polyurethane composite, Case Stud. Therm. Eng. 10 (2017)
fabricados com mistura de partículas de madeiras tropicais, Ambiente
2550–2559.
Construido 14 (3) (2014) 103–111.
 M.L. Sánchez et al. / Construction and Building Materials 228 (2019) 116749
[52] I.A. Ansari, G.C. East, D.J. Johnson, Structure-property relationships in natural
cellulosic fibres. Part 2: fine structure and tensile strength, Text. Res. J. 92 (4)
(2001) 331–348, https://doi.org/10.1016/j.csite.2017.10.012.
[53] A. Oushabi, S. Sair, F. Oudrhiri Hassani, Y. Abboud, O. Tanane, A. El Bouari, The
effect of alkali treatment on mechanical, morphological and thermal
properties of date palm fibers (DPFs): study of the interface of DPFe
Polyurethane composite, S. Afr. J. Chem. Eng. 23 (2017) 116–123.
[54] K. Kolarova, V. Vosmanska, S. Rimpelova, V. Svorcık, Effect of plasma treatment
on cellulose fiber, Cellulose 20 (2013) 953–961, https://doi.org/10.1007/
s1057001398630.
9
[55] Y. Sang, J.R. Zhao, Reduction of water absorption capacity of cellulose fibres for
its application in cementitious materials, J. Compos. Mater. 49 (22) (2015)
2757–2763, https://doi.org/10.1177/0021998314554123.
[56] H. Yang, R. Yan, H. Chen, D.H. Lee, C. Zheng, Characteristics of hemicellulose,
cellulose and lignin pyrolysis, Fuel 86 (2007) 1781–1788, https://doi.org/
10.1016/j.fuel.2006.12.013.
[57] A. Hanif, P. Parthasarathy, H. Ma, T. Fan, Z. Li, Properties improvement of fly ash
cenosphere modified cement pastes using nano-silica, Cem. Concr. Compos. 81
(2017) 35–48, https://doi.org/10.1016/j.cemconcomp.2017.04.008.