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JMRT D 23 09716 - R1
JMRT D 23 09716 - R1
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Cover Letter
MINISTÉRIO DA DEFESA
EXÉRCITO BRASILEIRO
DEPARTAMENTO DE CIÊNCIA E TECNOLOGIA
INSTITUTO MILITAR DE ENGENHARIA
(Real Academia de Artilharia, Fortificação e Desenho/1792)
The manuscript entitled " Characterization and Ballistic Performance of Hybrid Jute and
Aramid Reinforcing Graphite Nanoplatelets in High-Density Polyethylene Nanocomposites" is
being submitted for publication in Journal of Materials Research and Technology. On behalf of
my co-authors, I declare that there is no conflict of interest and the manuscript has not been
previously published or is currently under consideration for publication elsewhere. I also
confirm that all co-authors have read and approved the manuscript and, if accepted, it will not
be fully or partially published elsewhere without the written consent of the copyright holder.
The integration of natural lignocellulosic fibers and synthetic fibers for reinforcing polymeric
materials presents a compelling prospect for creating multifunctional hybrid materials and
structures with superior properties for advanced applications. Moreover, incorporating
graphite-based materials into these composites opens up opportunities for structural
functionalization and further property enhancement.
The present study focuses on optimizing the ballistic performance of newly developed
jute/aramid/high-density polyethylene hybrid nanocomposites by introducing graphite
nanoplatelets (GNP).
The number of citations for papers in this emerging field is encouraging, especially given its
novelty. One example is the graphene nanoplatelets-reinforced natural fiber composites, which
received 37 publications and over 245 citations between 2019 and 2022. This trend indicates a
rapidly expanding area of research that warrants further exploration and validates the
importance of the current investigation. Hence, this article has the potential to offer substantial
contributions to the field of Journal of Materials Research and Technology.
Best regards,
Ulisses Oliveira Costa
Military Institute of Engineering
Rio de Janeiro, Brazil
Response to Reviewers
Reviewer #1:
General comment: The manuscript has been written well but before acceptance
minor modification is required that has been given below:
Response: The authors would like to thank the Reviewers for the valuable
comments and suggestions on the structure and scientific aspects that contribute
to improve the manuscript. Amendments are provided accordingly. Responses to
each comment are listed below and all modifications/additions were marked as
Track changes in the revised version of the manuscript.
Comment (1): Authors need to thoroughly check the manuscript for grammatical
errors.
Response: The grammar of the manuscript is now revised in the improved
version of the manuscript. Whit the assistance of an English expert.
Comment (2): The introduction section has been written beautifully but need to
include recent published papers on nanocomposites like:
Effect of drilling process parameters on bearing strength of glass
fiber/aluminum mesh reinforced epoxy composites. Scientific Reports,
2023.
Response: The authors would like to thank for the important background paper
suggestions for the improvement of the manuscript. In the revised version these
references are now included.
Reviewer #2:
General comment: This manuscript presented an interesting work about the
characterization and ballistic performance of hybrid HDPE nanocomposites. The
work has potential. However, some points listed below need to be improved.
Response: The authors would like to thank the Reviewers for the valuable
comments and suggestions on the structure and scientific aspects that contribute
to improve the manuscript. Amendments are provided accordingly. Responses to
each comment are listed below and all modifications/additions were marked as
Track changes in the revised version of the manuscript.
Comment (1): Abstract: add some numerical results in the abstract.
Response: The authors agreed with the Reviewer’s comment. The Abstract of
the manuscript is now rewritten with some numerical results.
Comment (4): Section 3.1: in this section the authors observed an increase in
crystallinity but a decrease in crystal size after GNP addition. Please better
explain/discuss this interesting behavior in section 3.1.
Response: The authors understand the important point raised by the reviewer
and a better explanation in this regard is now included in the new version of the
manuscript.
Comment (5): Section 3.5: the authors said that: "at room temperature (RT=25
°C), the E' values for composites with low GNP concentrations, such as 0.10 wt%,
reached the highest storage modulus value (2.53 GPa). This represents an
increase of over 30% compared to the 20J/HDPE composite (1.90 GPa)." I
suggest better describe this result. What cause this increase in E' value?
Response: The Reviewer raised another important point, which deserves
attention. In the revised version of the manuscript, this result is now better
discussed and explained.
Revised Manuscript File Click here to view linked References
Ulisses Oliveira Costa1,*, Fabio da Costa Garcia Filho1 , Teresa Gómez-del Río2,
Édio Pereira Lima Júnior1, Sergio Neves Monteiro1, Lucio Fabio Cassiano Nascimento 2
1
Materials Science Department of Military Institute of Engineering (IME), Rio de Janeiro 22290-270, Brazil;
fabiogarciafilho@gmail.com (F.d.C.G.F.); edio@ime.eb.br (É.P.L.Jr.); snevesmonteiro@gmail.com (S.N.M.);
lucio@ime.eb.br (L.F.C.N.)
2Durability
and Mechanical Integrity of Structural Materials Group (DIMME), School of Experimental Sciences
and Technology, Rey Juan Carlos University, C/Tulipán, s/n. Móstoles, 28933 Madrid, Spain;
mariateresa.gomez@urjc.es Field Code Changed
* Correspondence: ulissesolie@ime.eb.br; Tel.: +55 -21982418125 Field Code Changed
1. Introduction
The technological development of polymers composite materials for engineering
applications serves a clear and fundamental purpose, namely, to reduce the cost and
weight of products [1-5], making them more competitive compared to metallic and
ceramic materials available in the market. This evolution benefits various industrial
sectors, such as construction, automotive, aerospace, and defense [1-5]. In particular,
the use of composites in defense materials, like ballistic armor for personal protection,
is crucial to ensure the safety and efficiency of vests and helmets [5].
In the specific context of ballistic vests and helmets, the predominant materials
are aramid and ultra-high molecular weight polyethylene (UHMWPE). Aramid is used
in the form of fabrics such as the commercial brands Kevlar® and Twaron®, produced
respectively by Dupont and Teijin. UHMWPE can be employed in the form of plates or
fabrics, resulting in products like Dyneema® or Spectra®. These materials are globally
recognized as the gold standard for protection against firearm shootings, blade stab,
explosion, and other impact events, thanks to their excellent mechanical properties,
high impact resistance, and energy absorption capacity [5-11]. Another favorable
characteristic of UHMWPE is its low density, making it floatable in water and,
consequently, providing greater comfort and agility to the user.
Additionally, a synthetic material like aramid fiber or its related fabric can undergo
various surface treatments and modifications to enhance properties and compatibility
with the polymeric matrices that bind to form composites. Some treatment methods
include chemical grafting (with acid or base), physical methods (like gamma radiation,
plasma, and ultraviolet), coating methods (using, for example, Polyethylene glycol-
PEG or epoxy resin), and nanostructural modifications (using nanoparticles like ZnO,
SiO2, TiO2, graphene, among others) [12-16].
Improving the surface of aramid fiber aims to enhance its chemical activity and
increase its roughness, enabling an excellent chemical bond and mechanical
interlocking between the fiber and the matrix. This process facilitates the interaction
between the fiber and the polymeric matrix, reducing the probability of failures such as
delamination, debonding, and slippage, while increasing the lifespan and safety of
composites [12].
However, it is essential to note that these cutting-edge materials come with a
relatively high cost, and additional treatments can further escalate production
expenses. Aware of this challenge, some researchers are focusing their efforts on
developing more cost-effective and environmentally viable hybrid composites, which
combine synthetic fibers with natural fibers for engineering applications [17-20].
A significant example is the study conducted by Meliande et al. [17], which
investigated the potential advantages of partial replacing aramid by curaua, a natural
lignocellulosic fiber (NLFs) in the tensile and impact properties of laminated hybrid
composites. Their results indicated that replacing 9 and 14 layers of aramid fabric by
2 and 3 layers of curauaá mat, resulted in a significantly advantageous reduction in all
tensile properties. Specifically, composites with approximately 33 vol.% volume of
aramid (10 layers) and 32 vol.% volume of curauaá mat (2 layers) in a matrix with about
35 vol.% volume of epoxy were considered the most promising for application in
ballistic helmets.
Similarly, the studies by Costa et al. [19] revealed that a hybrid nanocomposite
composed of 10 layers of NLFnatural jute fiber fabric (Corchorus capsularis) and 10 Formatted: Font: Italic
layers of aramid fabric, added with 0.10 wt.% of graphene nanoplatelets (GNP),
achieved a 2433% increase in mechanical toughness, 591% increase in tensile
strength, and a 462% reduction in ductility compared to plain composites containing
50% vol% of jute fiber reinforcing a high-density polyethylene (HDPE) matrix. These
results further highlight the potential of hybrid GNP added nanocomposites.
These novel hybrid nanocomposites have shown promising performance for
engineering applications [20]. NLFs, such as curaua and jute, are considered
promising candidates due to their many advantages, such as low density,
biodegradability, abundant availability, good damping properties, machinability, low
cost, ease of separation for recycling, enhanced energy recovery, and CO2 neutrality
[21]. Jute fiber or fabric is widely studied and recognized globally, making it a notable
choice for reinforcing polymer composites in various industries, including graphene-
based nanocomposites [20-24]. In this context, the present work investigated for the
first time the development of hybrid nanocomposites with a HDPE matrix functionalized
with GNP and reinforced with aramid and jute fabrics. The innovative aspect of the
present work is the combination of GNP functionalization, aramid, and jute
reinforcement within a HDPE matrix, exploring the potential synergies among these
elements. This exploration opens up new avenues for the production of hybrid
nanocomposites that are not only efficient in terms of ballistic protection but also
sustainable and cost-effective. The emphasis on sustainability is particularly
noteworthy, considering the environmental impact and cost challenges associated with
cutting-edge materials in the field of ballistic armor, specifically for helmets.
2. Methods
2.1. Materials and specimen preparation
From HDPE HE150 grade pellets sourced from Braskem [25], Brazil, and GNP
powder obtained from UCSGraphene, Brazil, a masterbatch (concentrate) was
produced through mechanical agitation, with an initial GNP concentration of 4.3 wt.%
by weight. Following this, three dilutions were conducted to acquire HDPE fractions
with GNP mass fractions of 0.10%, 0.25%, and 0.50 wt.%. Each dilution was executed
using the extrusion process in an interpenetrating and co-rotating twin-screw extruder,
Tecktril model DCT-2.
The extrusion conditions, as defined by Escocio et al. [26], were adopted,
including a screw rotation speed of 300 rpm, a feeder rotation speed of 15 rpm, and
tailored temperature profiles for the processing zones: 90°C for the first zone, 140°C
for the second to fifth zones, and 160-180°C for the sixth to ninth zones.
Subsequently, films with a uniform thickness of 300 μm were manufactured for
each condition using the hot compression molding technique. The processing took
place at a constant temperature of 170°C, employing a high-precision thermal press
Solab SL-11/15, Brazil. The films produced were associated to the following
nomenclature: 0.10%GNP/HDPE, 0.25%GNP/HDPE, and 0.50%GNP/HDPE.
In order to produce the hybrid nanocomposite plates, a laminating scheme was
adopted, where layers of fabrics were interleaved with HDPE films. For this purpose,
it was used an aramid fabric, commercially named Twaron®, provided by Teijin
Aramid, Brazil. The commercial grade used in the present work was the 410 g/m²
ballistic fabric, CT 736, with basket 2x2 weave. In addition, jute fabric was obtained
from the Brazilian manufacturer Sisalsul. According to Costa et al. [19], the jute fiber
fabric density was considered as 1.30 g/cm³. This parameter was important for
estimating the jute fiber fabric volume fraction. The as-received jute fabric consisted of
a simple weave, and it was cut to 120 × 120 mm dimensions and carefully dried in an
oven at 60 °C for 24 h to remove moisture. Consequently, it was manufactured hybrid
nanocomposites were manufactured by incorporating a combination of aramid and jute
fabrics reinforcement with a volume fraction of 50 vol.% content into the HDPE matrix,
resulting in plates measuring 120 x 120 x 10 mm. The process involved the use of 20
layers of fabric and 21 layers of HDPE films. During processing, the pressure was
gradually increased, adding one ton at a time, with each new pressure being
maintained for 1 min and followed by 30 s of degassing, until reaching a pressure of
13 tons. The cooling of the plates was conducted outdoors, allowing them to cool to
room temperature (RT) for demolding.
The Personnel Armor System for Ground Troops (PASGT) helmet was used as
a reference for the Jute/Aramid/GNP/HDPE hybrid nanocomposites. In the current
study, the number of layers corresponding to different reinforcements of synthetic and
natural fibers is a crucial aspect directly related to the hybrid composite design. The
traditional PASGT ballistic helmet has a final thickness of 8-10 mm [17,27], which is a
key criterion for achieving a density of 10 to 12 kg/m 2, equating to a stack weight of
approximately 200 g, and ensuring user comfort. Consequently, 20 layers of aramid
fabric were employed to simulate the PASGT helmet, representing a 100 vol.%
synthetic fiber composite.
Aiming to achieve cost-effectiveness, a strategic approach was adopted by
adjusting the number of aramid and jute layers in the hybrid nanocomposites as shown
in Table 1. The implementation followed a well-defined ratio: 20:0, 15:5, 10:10, and
5:15, corresponding to reduction fractions of 50%, 37.5%, 25%, and 12.5 vol.% by
volume of aramid in the composites, respectively. The nomenclature of the composites
is detailed in Table 1. Group 1 aims to analyze the influence of GNPs on the HDPE
matrix, while group 2 focuses on investigating the impact of reducing the aramid layers
in the hybrid nanocomposite. Table 1 the 0.X%p GNP indicates the best results
obtained from the group 1.
For pure HDPE, the XRD revealed the presence of two prominent peaks at 2θ =
25.16° and 2θ = 28.10°, corresponding to the (110) and (200) reflections of the
orthorhombic HDPE phase. Additionally, there are two weaker peaks at 2θ = 35.21°
and 2θ = 42.51°, which can be attributed to the (210) and (020) reflection planes,
respectively, as detailed by Xiang et al [35]. The XRD patterns of GNP/HDPE
nanocomposites displayed intriguing trends. In fact,: the intensities of the peaks at 2θ
≈ 25.16° and 2θ ≈ 28.10° decreased as the GNP content increased, while the
intensities of the peaks at 2θ ≈ 35.21° and 2θ ≈ 42.51° showed an opposite trend. This
indicates a complex interplay between HDPE and GNPs in these nanocomposites.
Formatted: Indent: First line: 0"
Several references, including Fischer, Wallner, and Pieber et al. [36], Kelkar et
al. [37], Nabiyev et al. [38], and Silva and Wiebeck [39], have collectively emphasized
the importance of the 1418.7 cm −1 band, often referred to as the "crystallinity band."
This specific band serves as a distinctive marker for the degree of orthorhombic
crystallinity in HDPE samples, and its significance has been well-established by Xiang
et al. [35].
Within the spectral data, other notable bands include those at 1060 and 1367.3
cm−1, which are attributed to the amorphous phase. Additionally, Raman peaks at
1060.8 and 1127.7 cm−1 correspond to symmetric and asymmetric stretching vibrations
of C–C bonds, while peaks at 2849.7 cm−1 and 2883.8 cm−1 indicate stretching of (CH3)
groups. Furthermore, the bands at 2907.7 cm−1 and 3068.5 cm−1 are assigned to the
(C−H group) [35-38].
In the Raman spectra of graphite-derived materials, four primary bands are
observed. The first and most prominent is the G band, peaking at around 1580 cm−1.
This band represents the E2g vibrational mode associated with the stretching of C-C
bonds within crystalline planes, serving as a hallmark of its graphitic nature.
The second, the D band, with a peak near 1350 cm −1, corresponds to vibrational
modes of carbon atoms with sp3 hybridization. This feature signifies defects in the
hexagonal structure, encompassing vacancies, pentagon, and heptagon rings as well
as edge effects, and functional groups. The ratio between the D and G band intensities,
termed the ID/IG ratio, serves as a parameter to gauge structural disorder in
carbonaceous materials. For the studied material, a low ID/IG ratio of 0.10 is derived, in
line with the findings of Moriche et al. [40] and an indicative of minimal structural
defects.
3.3. Morphology analysis
SEM and TEM analyses were conducted on the GNPs to elucidate the nanofillers'
structure. In Figures 3(a) and (b), a SEM image of the GNPs is displayed, revealing
that the agglomerates' average lateral size measures below 10 μm. Furthermore, these
agglomerates comprise over 10 layers, thereby validating the graphitic nature of the
GNPs.
(a) (b)
Figure 3. SEM images of the GNPs: (a) Lower magnification 5000x, and (b) higher magnification
30000x.
Figure 4 presents TEM images depicting the crystalline domains of the GNPs.
Figure 4(a) reveals a 20 nm single crystal, aligning well with the average crystal size
calculated by XRD. Moreover, Figures 4(b) and (c) showcase the distinctive sheet
morphology, indicating varying degrees of rolling; ranging from semi-rolled to fully
rolled. These images provide affirmation of a mixed array of structures, as inferred from
XRD analysis by Costa et al. [19].
(a)
(b) (c)
Figure 4. HR-TEM images of the GNPs (a) agglomerate of GNPs; (b) presents the GNP
monocrystalline structure semi-rolled; (c) displays GNP completely rolled
(c) (d)
Figure 5. SEM images of the GNP/HDPE nanocomposites: (a) HDPE, (b) 0.10%GNP/HDPE, (c)
0.25%GNP/HDPE, and (d) 0.50%GNP/HDPE.
Figure 6. DSC curves of 10°C/min: (a) cooling curve showing the exothermic pic representing the
crystalline temperature, and (b) heating curve showing the endothermic pic representing the melting
temperature.
Using the heating curves of the HDPE and GNP/HDPE films, the degree of
crystallinity for all composites was calculated using Equation (3). The obtained values
were as follows: HDPE (50.17%), HDPE/0.10%GNP (62.19%), HDPE/0.25%GNP
(63.71%), HDPE/0.50%GNP (75.10%). These results are closely aligned and follow
the same trend as the results obtained by XRD.
(a) (b)
(c)
Figure 7. DMA test results for the 20J/HDPE and 20J/GNP/HDPE composites, depicting the variation
of (a) storage modulus (E'), (b) loss modulus (E"), and (c) tan δ with temperature.
Furthermore, at room temperature (RT=25 °C), the E’ values for composites with
low GNP concentrations, such as 0.10 wt.%, reached the highest storage modulus
value (2.53 GPa). This represents an increase of over 30% compared to the 20J/HDPE
composite (1.90 GPa). The observed outcome can be ascribed to the reinforcing
impact of GNP, which induces a limitation in the mobility of HDPE chains, ultimately
leading to a strengthened interphase [40]. Additionally, the E’ values obtained in this
study align with those reported by other authors previously [40,41]. Lastly, it can be
observed that with an increase in GNP loading in the HDPE matrix, the E’ values tend
to decrease, approaching those of pure HDPE.
Another notable aspect is the sudden drops in E’ values, indicated by peaks in
Figure 7(b), occurring at -110 and 60 °C for all the curves. The first peak corresponds
to γ relaxation, marking the end of the glassy behavior region of HDPE. This drop could
potentially be linked to the transition to a rubbery amorphous region, characteristic of
increased mobility of chain segments in the amorphous phase of the polymer matrix,
i.e., the Tg. The second abrupt drop, α relaxation, is related to the thermal stability of
the composites, namely, the mobility of segments within the crystalline phase, which
becomes more thermally resistant with GNP incorporation [41].
In Figure 7(b), it is worth noting that for all HDPE composites reinforced with GNP,
the E” values were higher than those of the 20J/HDPE composite and were slightly
shifted towards higher temperatures. Indeed, E” represents a viscous response of the
material and is indicative of its tendency to dissipate applied mechanical energy [47].
In the case of composites, E” is often described as internal friction and should be
greater as the volume fraction of reinforcement increases [48]. This results in a larger
interfacial surface area between the load/polymer matrix. According to Mohanty et al.
[47], the molecular movement of the polymer due to structural heterogeneities like the
load interface would directly increase internal friction and, consequently, the value of
E”. However, with the increase in the amount of GNP in the HDPE matrix, the formation
of more agglomerates reduces the surface area between reinforcement and matrix. As
can be observed, the highest E” values were obtained for composites with low GNP
quantities (≥ 0.25 wt.%).
When it comes to composites, E” is often described as internal friction and tends
to be higher with a larger volume fraction of reinforcement [41]. This results in a greater
interfacial surface area between the load and polymer matrix. As Mohanty et al. [47]
indicate, the molecular motion of the polymer due to structural heterogeneities like the
load interface would directly increase internal friction and, consequently, the value of
E”. However, with the increase in the amount of GNP in the HDPE matrix, more
agglomerates are formed, which reduces the surface area between reinforcement and
matrix. Notably, the highest E” values were observed for composites with lower GNP
quantities (≥ 0.25 wt%).
Figure 7(c) depicts the variation of tanδ with temperature for the studied
composites. The tanδ represents the relationship between viscous energy dissipation
and elastic energy storage per cycle (tanδ = E′′/E′), and it is's a dimensionless number
linked to the material's mechanical damping. As Saba et al. [48] explain, a high tanδ
value indicates a material with significant deformation capacity.
Moreover, the temperature at the tanδ peak is considered the material's dynamic
Tg. According to the inset of Figure 7(c), the tanδ value displayed an increasing trend
as the GNP concentration in the HDPE matrix increased. It shifted from -113.80 °C to
-110.22 °C for the composite with 0.50% GNP. This highlights the stiffer behavior of
composites with GNP incorporated into the HDPE matrix.
In comparison to the 20J/HDPE composite, the GNP-functionalized composites
exhibited peaks of tanδ with lower magnitudes, indicating a decreasing trend as the
incorporated GNP quantity increased. This behavior suggests that the 20J/HDPE
composite has a weak interfacial bond between the fibers and the matrix, allowing it to
dissipate more energy, resulting in a higher damping peak magnitude compared to a
material with a strongly bonded interface. However, after HDPE functionalization with
GNP, the magnitude of tanδ peaks decreased, signifying an improvement in the
interfacial bond and a subsequent reduction in energy dissipation capacity.
Figure 8(a) illustrates that as the number of layers of Twaron®™ aramid fabric
increases, the E’ values at 35 °C decrease. This could be due to the greater flexibility
of aramid fabric compared to jute fabric [47]. For instance, comparing the E’ values of
20J/0.10%GNP/HDPE nanocomposites and 20A/0.10%GNP/HDPE nanocomposites,
a reduction of over 70% can be calculated. Additionally, the same two relaxation
phenomena observed in the E’ curves of Figure 7(a) were observed.
(a) (b)
(c)
Figure 8. DMA test results for the J/A/GNP/HDPE composites, showing the variation of (a) storage
modulus (E'), (b) loss modulus (E"), and (c) tan δ with temperature.
However, for the E” values found in Figure 8(b), a considerable increase is seen
compared to the non-aramid composites of Figure 7(b). The hybrid
10J/10A/0.10%GNP/HDPE nanocomposite reached a peak E” around 60 °C of 230.32
MPa, representing an increase of 16.47% compared to the 20J/0.10%GNP/HDPE
nanocomposite (197.75 MPa). Also, a peculiar behavior around 15 °C is observed for
the hybrid nanocomposites 10J/10A/0.10%GNP/HDPE and 20A/0.10%GNP/HDPE.
This might have occurred due to slipping or accommodation between the fabric layers
during the test.
Regarding the tan(δ) values shown in Figure 8(c), it is noticeable that concerning
the maximum value, the aramid-containing composites showed an increase compared
to the non-aramid nanocomposites of group 1. This points to an improvement in the
energy dissipation capacity of the HDPE/GNP/Jute/Aramid composites. In relation to
Tg, the hybrid 10J/10A/0.10%GNP/HDPE nanocomposite presented the highest value
at -110.40 °C, similar to the 20J/0.10%GNP/HDPE composite (-110.22 °C).
Additionally, with an increase in the number of aramid fabric layers, there was a
decreasing trend in Tg values for the hybrid nanocomposites.
3.6. Residual velocity results
Table 3 provides a summary of all the properties obtained from the residual
velocity test for all the composite conditions analyzed in this study. These properties
encompass the projectile's impact velocity, the residual velocity after impact, the
energy absorbed by the composite, and the limit velocity.
Table 3. Summary of properties obtained from the residual velocity test for all the composites studied
in this work.
Vimp VRes Eabs VLim
Material
(m/s) (m/s) (J) (m/s)
20J/HDPE 423.40±6.10 402.17±7.56 69.50±5.53 130.79±5.54
20J/0.10%GNP/HDPE 421.61±2.87 401.26±3.28 66.98±3.39 129.37±3.25
20J/0.25%GNP/HDPE 419.86±2.00 401.41±2.44 62.94±7.44 124.78±6.38
20J/0.50%GNP/HDPE 421.47±2.80 402.91±3.14 64.66±2.92 127.12±2.88
15J/5A/0.10%GNP/HDPE 421.87±5.74 377.66±6.13 141.36±9.81 187.90±6.50
10J/10A/0.10%GNP/HDPE(*) 422.59±2.20 262.94±74.93 419.84±146.45 320.13±55.60
5J/15A/0.10%GNP/HDPE(*) 418.54±5.25 158.01±42.24 659.41±55.83 405.72±17.54
20A/0.10%GNP/HDPE(**) 422.48±2.16 0 713.96±7.29 422.48±2.16
(*) Partial perforation occurred, (**) No perforation occurred
Regarding this last parameter, the absorbed energy values, they were utilized
along with the kinetic energy equation to determine the velocity required to prevent
composite perforation.
Table 3 also presents the results of the nanocomposites absorbed energy (Eabs) Formatted: Subscript
after the impact of a 9 mm caliber projectile for the nanocomposites without aramid
fibers. However,. In fact, no evidence of modifications caused by GNP incorporation in
HDPE was found. As a result, the ANOVA analysis demonstrated that the values of
residual velocities are statistically equivalent with a 95% confidence level, as the
calculated F value of 3.14 < critical F value of 3.24.
This finding suggests that composites composed of 20 layers of jute fabric are
not suitable for applications in ballistic helmets. This is due to the fact that the amount
of absorbed energy is significantly lower in comparison to the impact energy, rendering
them insufficient to provide the required protection.
However, as aramid fabric layers were incorporated, a notable increase in energy
absorption capacity was observed, as clearly evidenced in Table 3. This trend was
further corroborated by ANOVA, where the calculated F value (86.97) significantly
exceeded the critical F value (2.87). According to the Tukey test, Table 4, this
significant difference was observed only for hybrid nanocomposites with more than 10
layers, with an average difference (d.m.s) of 137.43 J.
Table 4. Tukey Test Results for Absorbed Energy Values of Hybrid Nanocomposites.
20J/
15J/5A/0.10%GN 10J/10A/0.10%G 5J/15A/0.10%GN 20A/0.10%GN
0.10%GNP/
P/HDPE NP/HDPE P/HDPE P/HDPE
HDPE
20J/
0.00 74.39 352.86 592.43 646.98
0.10%GNP/HDPE
15J/5A/0.10%GN
74.39 0.00 278.47 518.05 572.60
P/HDPE
10J/10A/0.10%G
352.86 278.47 0.00 239.57 294.12
NP/HDPE
5J/15A/0.10%GN
592.43 518.05 239.57 0.00 54.55
P/HDPE
20A/0.10%GNP/H
646.98 572.60 294.12 54.55 0.00
DPE
Figure 10. Appearance of hybrid nanocomposites before and after the shootings: (a) Composite plates
from Group 2 before the shootings; (b) HDPE/GNP/10Jute/10Aramid plate after multiple shootings; (c)
HDPE/GNP/5Jute/15Aramid plate after a single shooting; and (d) HDPE/GNP/20Aramid plate after a
single shooting. (Author).
Additionally, in the delamination areas, the ease with which the fabric loses its
structure, resulting in the opening of the weave, can be observed, as depicted in Figure
10(c). This occurrence can be attributed to the lesser adhesion of aramid fibers with
into the polymer matrix compared to jute fibers combined with the GNP/HDPE matrix,
as exemplified in Figure 10(d).
Finally, it is relevant to compare the limit velocity (VLim) values in Table 3 achieved Formatted: Subscript
by the hybrid nanocomposites with the ballistic levels established by the NIJ 0106.01
standard [51], in order to demonstrate the potential of each composite for ballistic
helmet applications. As specified in the mentioned standard, considering an 8 g, 9 mm
caliber projectile, the hybrid nanocomposites with 10 layers reached ballistic level II-A,
while those with 15 and 20 layers achieved level IIIA, even after multiple shootings.
3.7. Cost effectiveness analysis
Considering the provided existing information, a cost and weight analysis per
helmet was conducted, using the PASGT helmet as a reference, with an area of 0.14
m² and an aerial density of 11.2 kg/m², as per Folgar [52]. In this context, Table 54 was
generated, containing the recorded costs and weights of each helmet produced under
the conditions of the hybrid nanocomposites studied in this work. The densities and
prices of each material were obtained from respective commercial companies, such as
Braskem, Sisalsul, Teijin Aramid, and UCSgraphene.
For this purpose, nanocomposite plates with 20 layers of fabric were considered,
with a matrix of 50 vol.% volume of HDPE and 50 vol.% volume of fabric reinforcement.
This approach allowed estimating the weight and cost of each nanocomposite based
on their specific configurations, in accordance with the PASGT model, as described by
Folgar [52].
Table 54. Cost and weight estimates for helmets manufactured using the hybrid nanocomposites
studied in this work.
Cost/unit (USD)
20A/0.10 5J/15A/0.10 10J/10A/0.1 15J/5A/0.10 20J/0.10
Mate Price Weight/
Density %GNP/ %GNP/ 0%GNP/ %GNP/ %GNP/
rial (USD)/kg helmet (kg)
HDPE HDPE HDPE HDPE HDPE
HDP 0.948
2.64 0.66 1.75 1.75 1.75 1.75 1.75
E (g/cm³)
320
Jute 8.70 0.90 0.00 1.95 3.90 5.85 7.80
(g/m²)
Ara 410
60.00 1.15 68.88 51.66 34.44 17.22 0.00
mid (g/m²)
GNP 1.993.30 7.00E-04 1.40 1.40 1.40 1.40 1.40
Total 72.03 56.76 41.49 26.21 10.94
Decrease
- 21.21 42.41 63.61 84.81
in Cost (%)
Weight/
1.81 1.75 1.69 1.62 1.56
helmet (kg)
Decrease in
3.60 7.47 11.64 16.15
weight (%)
Based on the data presented in Table 54, it was observed that the inclusion of 5
layers of jute fabric results in a cost reduction of over 20%. Additionally, the addition of
5 layers of jute fabric leads to a reduction of over 3% in the weight of the
nanocomposites. This outcome underscores the feasibility of using these materials in
ballistic helmet applications, as the hybrid nanocomposite 5J/15A/0.10%GNP/HDPE
maintains the same level of protection as the 20A/0.10%GNP/HDPE nanocomposite.
Consequently, the hybrid nanocomposite 10J/10A/0.10%GNP/HDPE presents a
cost reduction of over 40%. Similarly, it can be observed that the hybrid nanocomposite
10J/10A/0.10%GNP/HDPE demonstrates a weight reduction of over 7% compared to
helmets produced with 20A/0.10%GNP/HDPE. This emphasizes the significant
potential of these hybrid materials, particularly the GNP incorporated nanocomposites,
for applications in ballistic helmets.
4. Conclusions
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Declaration of Competing Interest
Declaration of interests
☒The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
Figure 1 Click here to access/download;Figure;Imagem1.png
Figure 2 Click here to access/download;Figure;Graph3.png
Figure 3a Click here to access/download;Figure;Imagem3.jpg
Figure 3b Click here to access/download;Figure;Imagem3b.jpg
Figure 4a Click here to access/download;Figure;Imagem4a.jpg
Figure 4b Click here to access/download;Figure;Imagem4b.jpg
Figure 4c Click here to access/download;Figure;Imagem4c.jpg
Figure 4d Click here to access/download;Figure;Imagem4d.jpg
Figure 5a Click here to access/download;Figure;Imagem5a.png
Figure 5b Click here to access/download;Figure;Imagem5b.png
Figure 5c Click here to access/download;Figure;Imagem5c.png
Figure 6a Click here to access/download;Figure;Imagem6a.png
Figure 6b Click here to access/download;Figure;Imagem6b.png
Figure 7a Click here to access/download;Figure;Imagem7a.png
Figure 7b Click here to access/download;Figure;Imagem7b.png
Figure 7c Click here to access/download;Figure;Imagem7c.png
Figure 8a Click here to access/download;Figure;Imagem8a.png
Figure 8b Click here to access/download;Figure;Imagem8b.png
Figure 8c Click here to access/download;Figure;Imagem8c.png
Figure 9a Click here to access/download;Figure;Figure 9a.jpeg
Figure 9c Click here to access/download;Figure;Figure 9c.jpeg
Figure 9d Click here to access/download;Figure;Figure 9d.jpeg
Figure 9b Click here to access/download;Figure;Figure 9b.jpeg
Figure 10a Click here to access/download;Figure;Figure 10a.tif
Figure 10b Click here to access/download;Figure;Figure 10b.tif
Figure 10c Click here to access/download;Figure;Figure 10c.tif
Figure 10d Click here to access/download;Figure;Figure 10d.tif
Table 5 Click here to access/download;Table;Table 5.docx
Table 5. Cost and weight estimates for helmets manufactured using the hybrid nanocomposites
studied in this work.
Cost/unit (USD)
Price 20A/0.10 5J/15A/0.1 10J/10A/0. 15J/5A/0.1 20J/0.10
Mat Densit Weight/
(USD)/k %GNP/ 0%GNP/ 10%GNP/ 0%GNP/ %GNP/
erial y helmet (kg)
g HDPE HDPE HDPE HDPE HDPE
HDP 0.948
2.64 0.66 1.75 1.75 1.75 1.75 1.75
E (g/cm³)
320
Jute 8.70 0.90 0.00 1.95 3.90 5.85 7.80
(g/m²)
Ara 410
60.00 1.15 68.88 51.66 34.44 17.22 0.00
mid (g/m²)
GNP 1.993.30 7.00E-04 1.40 1.40 1.40 1.40 1.40
Total 72.03 56.76 41.49 26.21 10.94
Decrease
- 21.21 42.41 63.61 84.81
in Cost (%)
Weight/
1.81 1.75 1.69 1.62 1.56
helmet (kg)
Decrease in
3.60 7.47 11.64 16.15
weight (%)
Table 2 Click here to access/download;Table;Table 2.docx
Table 2. Summary of properties obtained from the residual velocity test for all the composites
studied in this work.
Vimp VRes Eab VLim
Material
(m/s) (m/s) (J) (m/s)
20J/HDPE 423.40±6.10 402.17±7.56 69.50±5.53 130.79±5.54
20J/0.10%GNP/HDPE 421.61±2.87 401.26±3.28 66.98±3.39 129.37±3.25
20J/0.25%GNP/HDPE 419.86±2.00 401.41±2.44 62.94±7.44 124.78±6.38
20J/0.50%GNP/HDPE 421.47±2.80 402.91±3.14 64.66±2.92 127.12±2.88
15J/5A/0.10%GNP/HDPE 421.87±5.74 377.66±6.13 141.36±9.81 187.90±6.50
10J/10A/0.10%GNP/HDPE(*) 422.59±2.20 262.94±74.93 419.84±146.45 320.13±55.60
5J/15A/0.10%GNP/HDPE(*) 418.54±5.25 158.01±42.24 659.41±55.83 405.72±17.54
20A/0.10%GNP/HDPE(**) 422.48±2.16 0 713.96±7.29 422.48±2.16
(*) Partial perforation occurred, (**) No perforation occurred
Table 4 Click here to access/download;Table;Table 4.docx
Table 4. Tukey Test Results for Absorbed Energy Values of Hybrid Nanocomposites.
20J/
15J/5A/0.10%G 10J/10A/0.10%G 5J/15A/0.10%G 20A/0.10%GN
0.10%GNP
NP/HDPE NP/HDPE NP/HDPE P/HDPE
/HDPE
20J/
0.10%GNP/HDP 0.00 74.39 352.86 592.43 646.98
E
15J/5A/0.10%G
74.39 0.00 278.47 518.05 572.60
NP/HDPE
10J/10A/0.10%G
352.86 278.47 0.00 239.57 294.12
NP/HDPE
5J/15A/0.10%G
592.43 518.05 239.57 0.00 54.55
NP/HDPE
20A/0.10%GNP/
646.98 572.60 294.12 54.55 0.00
HDPE
Table 1 Click here to access/download;Table;Table 1.docx