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Vol. 7. Num. 4.October - December 2018
Pages 403-616
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Vol. 7. Num. 4.October - December 2018
Pages 403-616
Original Article
DOI: 10.1016/j.jmrt.2018.09.004
Open Access
Ballistic behavior of a hybrid composite reinforced with curaua and aramid fabric subjected to ultraviolet radiation
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Anderson Oliveira da Silva
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anderson.q.ao@gmail.com

Corresponding author.
, Karollyne Gomes de Castro Monsores, Suzane de Sant’ Ana Oliveira, Ricardo Pondé Weber, Sergio Neves Monteiro
Military Institute of Engineering – IME, Department of Materials Science, Praça General Tibúrcio 80, Urca, 22290-270 Rio de Janeiro, Brazil
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Figures (7)
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Tables (4)
Table 1. Degree of crosslinking and swelling ratio of orthophthalic polyester resin before and after UV irradiation.
Table 2. Oxidation indices obtained by the peak intensities of 1639cm−1 and 1537cm−1 of aramid fabric, normalized by the peak intensity of 821cm−1, before and after UV irradiation.
Table 3. Oxidation indices obtained by the peak intensities of 1727cm−1 and 1033cm−1 of curaua mat, normalized by the peak intensity of 2917cm−1, before and after UV irradiation.
Table 4. Average ballistic energy as a function of the areal density (ρA).
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Abstract

Mobile ballistic armors, particularly those intended for personal protection, are also designed with lowest possible weight. Composite materials are the best choice for this kind of application, especially laminated composites reinforced with high-performance fibers or fabrics. Owing to environmental problems, research works on hybrid composites based on natural instead of synthetics fibers is already a promising line of investigation. These composites, when used outdoors, are exposed to ultraviolet (UV) radiation and some properties and applied behavior may change. Therefore, this work investigated the ballistic behavior of a thermoset polyester resin laminated hybrid composite reinforced with a natural fiber mat and aramid fabric after exposure to UV radiation. The mat was produced with curaua fiber, one of the strongest natural fibers. Infrared spectroscopy analysis and determination of the degree of cross-linking, to identify possible structural changes in the curaua mat, are performed after two different exposure times to UV radiation The mechanism of failure related to the ballistic impact is analyzed by visual inspection. The results show that the composite is influenced by UV radiation, which affects the ballistic performance due to delamination on the interface of plies as well as chain scission on curaua fibers and increasing crosslinking of the polyester resin. The delamination was attributed to a low interfacial energy between the polyester matrix and curaua fibers.

Keywords:
Hybrid composite
Curaua mat
Aramid fabric
Polyester matrix
Armor
Ultraviolet radiation
Full Text
1Introduction

Ballistic armors are designed to resist a specific projectile threat with efficient weight/protection ratio, i.e., highest ballistic strength with the lowest weight. In the case of personal and vehicular protection, the lightness of the armor is of uppermost concern in terms of mobility. Composite materials might be a choice for this kind of application [1,2]. These materials are usually reinforced with fabrics of high-performance synthetic fibers, because of their low density, high Young modulus, high strength and excellent capability for absorbing the projectiles’ kinetic energy [3]. With the current attention to environmental issues, a significant growth of researches on composites reinforced with natural lignocellulosic fibers (CRNF) is revealing advantages that these fibers present when compared to synthetic ones [4–11]. In particular, examples of natural fiber composites are emerging as proposals to produce sustainable materials [12–16]. These examples serve as motivation for possible studies on the use of hybrid composites in different applications, including ballistics.

The development of CRNF with hybrid participation of synthetic fibers in many cases will need environmental effects to be considered. Indeed, humidity, temperature, biological attack and radiation might induce degradation associated with changes in molecular structure, which could significantly impair the composite properties. Ionizing radiation, such as ultraviolet (UV) rays, gamma rays, X-rays, accelerated electrons and ion beam, leads to scission of the main macromolecular chains as well as crosslinking with the concomitant formation of covalent bonds among synthetic or natural polymers [17]. In particular, UV radiation might significantly affect natural fibers and could also be relevant in hybrid composites due to both fibers scission and crosslink in the polymer matrix [18]. These combined effects decrease the fiber/matrix adhesion and induce delamination. As a matrix-dominated fault mechanism, delamination normally impairs the composite mechanical properties [19]. However, delamination might also play a positive role in the ballistic behavior by dissipating part of the impact energy.

Fig. 1 shows schematically the ballistic failure mechanism proposed by Yu et al. [20] upon the impact of a projectile, from partial penetration to complete perforation.

Fig. 1.
(0.11MB).

Behavior of fiber-reinforced aramid composites after impact: (a) and (b) partial penetration; (c) complete perforation [20].

Partial penetration occurs in two stages. First, the impact produces fiber breaking by shear, Fig. 1(a); after that, the kinetic energy of the projectile is absorbed and its speed decreases due to fiber stretching, bulging and layer delamination, Fig. 1(b). Complete perforation is associated with fiber breaking, which also decreases the projectile speed due to energy absorption and is followed by plastic deformation, showing that ballistic failure is controlled predominantly by both delamination and the tensile stress at break of the reinforcing fibers, Fig. 1(c) [20].

The present work investigated a hybrid CRNF composed of a polyester matrix reinforced with a natural mat made of curaua fiber and an aramid fabric. Among the traditional Brazilian natural lignocellulosic fibers, those extracted from the curaua plant (Ananas erectifolius) of Amazonian origin, stands out in the engineering applications for its high mechanical strength and stiffness, attributed mainly to the high content of cellulose (70% cellulose content), degree of polymerization (conferred to approximately 21% of hemicellulose 8% of lignin) and low fibrillary angle [6]. Environmental effects associated with photodegradation and biodegradation in EPS/curaua fiber composites [21] as well as accelerated aging on the mechanical properties of curaua/glass fiber hybrid composites [22] have already been primarily investigated. The choice for the synthetic aramid fabric in the present hybrid composite was based in the worldwide application for ballistic protection. In fact, the aramid fabric, Kevlar™ or Twaron™ (commercial trade marks), is known by its superior mechanical properties such as tensile strength, 3600–4100MPa, and elastic modulus, 131GPa, associated with relatively low density of 1.44g/cm3[23].

In this work, the degradation process in a hybrid polyester composite reinforced with curaua mat and aramid fabric subjected to UV radiation, is evaluated in terms of dissipated energy from the impact of projectile in ballistic tests. The composite performance is also evaluated by physical and chemical analyses. The type of failure, which occurred before and after different times of UV irradiation exposure is investigated to disclose mechanisms responsible for changes in both the microstructure and properties.

2Materials and methods

Laminated hybrid composites were produced with 6wt% polyamide aromatic (aramid) fabrics, 34wt% curaua fabrics and 60wt% thermoset polyester resin (matrix). Curaua mats were supplied by Pematec Triangel Company, the aramid fabrics by Teijin Aramid Company and the polyester resin by Resinpoxy Company, Brazil. Both curaua mats and aramid fabrics were dried in a stove at 60°C for 24h. The curaua mats were first compressed under 2 ton in a model Skay-15 hydraulic press for better accommodation of the fibers. Rectangular 150×120×12mm plies of both curaua mats and aramid fabrics were positioned together with still fluid polyester resin inside a steel mold, according to the distribution of layers schematically shown in Fig. 2. Hybrid laminated composites were obtained after uniaxial pressing under 5 ton of load in the aforementioned hydraulic press. Curing occurred under pressure for 24h. It is important to notice in Fig. 2 that curaua plies were placed at the surfaces of the hybrid composite plate, just covered by a thin (∼1mm) layer of polyester. In this way, the aramid fabrics were distant ∼6mm from the plate surfaces and, consequently, much less affected by UV radiation.

Fig. 2.
(0.09MB).

Schematic representation of the hybrid composite preparation.

The exposition of samples to UV radiation was performed by using an accelerated aging system for non-metallic materials with ultraviolet “B” rays (UV-B), following the standard guidelines of ASTM G-154 [24], during 300 and 600h for both sides, remaining them in direct contact with air. They have been located at 5cm of distance away from the UV sources emitting a spectrum peaking at the wavelength of 306nm.

Infrared spectroscopy analyze was performed on an IS50 Smart ITR Spectrometer in the range 400–4000cm−1. This analysis was aimed at evaluating structural changes in the macromolecules of the irradiated material to correlate the UV radiation times with the possible crosslinking of the thermoset resin (matrix) and chain scission of the curaua fibers. The molecular change of curaua has been studied using the peaks in 1727cm−1 and 1033cm−1 that are attributed, respectively, to stretching of the CO functional group and C–O–C on the molecular chain of the curaua fiber [17].

The amount of polyester resin crosslinked by the action of UV radiation was determined by the calculation of the crosslinking degree, before and after irradiation. This was performed by the extraction of the non-crosslinked resin in a Soxhlet type extractor, following the ASTM D 2765 [25] standard with some modifications. Tetrahydrofuran (THF) grade PA was used as the solvent for 6h under reflux (189 –192°C) at the rate of 40 drops per minute. Drying of the insoluble gel, after complete extraction of the uncrosslinked components, was performed inside a stove at 110°C for 12h until the mass remained constant. The calculation of the insoluble fraction of the material was performed according to Eq. (1), where Ws is the mass of the non-soluble sample, after drying, in grams; Wi is the initial sample mass (before extraction) in grams, and Wo is the mass of the cage.

The swelling ratio of the polymer matrix was also determined according to Eq. (2). This ratio corresponds to the absorption of the solvent by the polymer, which is directly related to the number of crosslinks present in the polymer [26]. Where Wu is the mass of the wet sample with the cage.

The ballistic tests were carried out according to the NIJ Standard 0108.01 [27] level II (9mm ammunition), using projectiles fired from a weapon (gun barrel) on targets 5m away, at an incident angle of 0°. Fig. 3 illustrates schematically the ballistic test setup located at the Brazilian Army shooting range facility (CAEx, Rio de Janeiro).

Fig. 3.
(0.1MB).

Schematic view of the ballistic test setup [28].

The ballistic performance of the armor was evaluated considering the energy absorbed by the composite, calculated by Eqs. (3) and (4), using the residual and impact velocity, obtained by Doppler radar model Weibel SL-520P, after complete perforation. For each condition (non-irradiated, irradiated 300h and irradiated 600h), five composites were tested, each with one shot.

where EL is the absorbed energy, Ei the impact energy and ER the residual energy.

The damage produced by the shot, in terms of the layer deformation, the occurrence of punching or cutting of the yarns and the delamination around the point of impact was analyzed by visual inspection. Scanning electron microscopy (SEM) observations were performed in a model Quanta FEG 250 FEI microscope with secondary electrons operating at 15kV. Samples were previously coated with platinum.

3Results and discussion

Table 1 shows the variation of the degree of crosslinking (expressed as percentage of gel) and the swelling content of the orthophthalic polyester resin as a function of the time of exposure to UV radiation.

Table 1.

Degree of crosslinking and swelling ratio of orthophthalic polyester resin before and after UV irradiation.

Condition of the polyester resin  Average degree of crosslinking %  Average swelling ratio 
Non-irradiated  96.4±1.7  1.41 
300h of UV irradiation  95.6±2.1  1.41 
600h of UV irradiation  97.1±0.6  1.34 

The results in Table 1 reveal, for all conditions, that only around 4% of polyester resin did not undergo crosslinking during the curing process. This suggests a failure in the production of the composite, i.e., lack of interaction between the curing agent and the liquid resin. It can also be seen that the material exposed to 300h did not produce more cross bonds than the non-irradiated composite, as shown by the swelling ratio of 1.41 for both conditions. However, after 600h of irradiation the number of cross bonds increased, as observed by the swelling ratio of 1.34. This raise on links suggests that the UV radiation acts as the initiator for the cure of the monomers not previously crosslinked, just after 600h, producing a higher amount of crosslinking in the polymer and resulting in a stiffer composite [29]. Actually, this increase in crosslinking makes the resin more brittle, providing a decrease in interfacial energy and increasing the probability of delamination.

The degradation promoted by UV radiation in hybrid CRNFs occurs on the surface of the polyester and curaua fiber macromolecules in a micrometric scale. By contrast, significant changes in the aramid fabric layer were not observed [30]. Table 2 shows the oxidation indices evaluated by the normalized peak intensities for Amide I (1639cm−1) and Amide II (1537cm−1), as a function of peak intensity of 821cm−1, considered unaffected by irradiation [31,32]. It can be seen that the intensities at both peaks varied as compared to the non-irradiated material. This indicates that carboxylic or aldehyde groups were possibly generated after cleavage (C–N) of the main chain. In the case of the 600h irradiation, this process was attributed to photo-oxidation at the fiber surface [33].

Table 2.

Oxidation indices obtained by the peak intensities of 1639cm−1 and 1537cm−1 of aramid fabric, normalized by the peak intensity of 821cm−1, before and after UV irradiation.

Condition of the aramid fabric  Oxidation indices (1639/821)  Oxidation indices (1537/821) 
Non-irradiated  0.527  0.659 
300h of UV irradiation  0.541  0.746 
600h of UV irradiation  0.512  0.659 

Fig. 4 presents the FTIR spectra of the curaua fabric before and after UV irradiation. In this figure, the intensities of absorbance peak associated with the C–O–C group are shown expressed as a function of the characteristic wave number of the material [34,35]. Table 3 presents the oxidation indices obtained by peak intensities of 1727cm−1 and 1033cm−1, normalized by the peak intensity of 2917cm−1, before and after UV radiation.

Fig. 4.
(0.13MB).

Curaua fiber spectra before and after different times of UV irradiation.

Table 3.

Oxidation indices obtained by the peak intensities of 1727cm−1 and 1033cm−1 of curaua mat, normalized by the peak intensity of 2917cm−1, before and after UV irradiation.

Condition of the curaua mat  Oxidation indices (1727/2917)  Oxidation indices (1033/2917) 
Non-irradiated  0.658  3.870 
300h of UV Irradiation  0.467  1.996 
600h of UV Irradiation  0.416  1.154 

According to Table 3, the decrease of both peak intensities suggests the occurrence of scission in C–O–C and CO groups, giving rise to lower molecular weight. As a consequence, the curaua mat becomes brittle, which affects the hybrid composite ballistic behavior [17].

Table 4 presents the absorbed energy by the hybrid composite before and after UV irradiation on the ballistic tests. Within the respective precisions (standard deviation) both UV irradiation times are associated with similar absorbed energies, relatively lower (∼14%) than that absorbed by the non-irradiated samples.

Table 4.

Average ballistic energy as a function of the areal density (ρA).

Condition of the composite  ρA (kg/m2Absorbed energy (J) 
Non-irradiated  13.36±0.18  140.01±16.24 
300h of UV irradiation  13.04±0.02  105.93±13.49 
600h of UV irradiation  12.58±0.20  120.51±09.91 

As the Doppler radar did not capture the impact velocity of the projectile at the composite, this velocity was assumed to be the same at the exit of the gun barrel in Fig. 3[36]. The results in Table 4 show that the ballistic resistance of the composite decreased with UV irradiation and the absorbed energy (EL), Eq. (4), associated with the same areal density (ρA), varies with the increasing UV irradiation time.

The decrease observed in the ballistic performance of the hybrid composite after UV exposure could be mainly attributed to the decrease in the molecular weight of the curaua mat, Fig. 4. A small contribution to this decrease might also be assigned to the increase in the amount of crosslinks of the polyester matrix, shown in the degree of swelling for 600h of irradiation, Table 1. However, the composite subjected to 600h of UV radiation presented better ballistic performance than those subjected to 300h of exposure. This suggests that the possible intermolecular bonds (hydrogen bonds between the natural fiber surfaces/matrix) generated after the UV irradiation, promote a greater rigidity to the surface of the material. This gives rise to intralaminar faults that propagate throughout the composite body and, consequently, result in delamination [17,37].

The macro and microscopic analyses allowed the identification of possible failure mechanisms in the laminated composite. Fig. 5 presents the cross-section of the impacted composite, before and after the UV irradiation.

Fig. 5.
(0.58MB).

Cross section of composites after ballistic tests: (a) non-irradiated; (b) 300h of UV irradiation; (c) 600h of UV irradiation and (d) SEM micrograph of the 600h UV irradiated sample.

In this figure, it is observed that complete ballistic perforation occurred for all conditions. In Fig. 5(a) it is also noted that non-irradiated composite absorbed the impact energy through the rupture of the fibers (curaua and aramid), followed by the plastic deformation of the fibers. The SEM micrograph in Fig. 6 shows that the fibers are ruptured with slight stretches at their ends (microfibrils). This confirms the fact that the fibers’ plastic deformation and their tensile strength control this type of failure in both non-irradiated curaua mat and aramid fabric.

Fig. 6.
(0.38MB).

SEM micrographs of the fracture surface of non-irradiated: (a) curaua fibers in the mat and (b) aramid fibers in the fabric.

By contrast, as shown in Fig. 5(b)–(d), it should be noted that, unlike non-irradiated composites, the irradiated ones have delamination after ballistic impact. This delamination is possibly related to increased crosslinking of the polymer chains after exposure to ionizing radiation, yielding a more rigid and less tough resin. This rigidity, which can be translated into less plastic deformation in relation to the fibers, increases the probability of delamination occurring in the composite [38,39]. This results in energy dissipation upon impact and is, therefore, not considered to be harmful to the ballistic behavior of the composite.

In Fig. 7, it is observed by SEM that the irradiated curaua fibers in the mat tends to deteriorate with the projectile's friction, as compared to the non-irradiated ones, with regions possibly degraded by pyrolysis. By contrast, the irradiated aramid fibers in the fabric presented a higher amount of fibrillation ascribed to a decrease in plasticity.

Fig. 7.
(0.31MB).

SEM micrographs of the fracture surface of: (a) curaua fibers in the mat irradiated with 300h, showing regions degraded by pyrolysis and (b) aramid fibers in the fabric irradiated with 600h.

Both processes are occurring in the composite due to UV radiation, but the lowering ballistic resistance due to the curaua decrease molecular weight prevails over the delamination process on these composites for the studied times of exposition.

4Conclusions

  • Results of ballistic tests of hybrid polyester matrix composites reinforced with plies of curaua mat, near the surface, and aramid fabric, in the interior of plate samples, revealed the effect of ultraviolet (UV) radiation for 300 and 600h of exposure.

  • The absorbed ballistic energy from the impact of a 9mm ammunition displayed similar values for both 300 and 600h UV irradiated composites. These values were found to be around 14% lower than that for the non-irradiated composite.

  • UV radiation exposure improved the crosslinking degree of the polyester matrix, which became more rigid with less plastic deformation in association with a decrease in its capacity to absorb the impact energy.

  • As for the curaua mats near the hybrid composite surface, fiber macromolecular scission due to UV irradiation causes brittleness of the mat, which reduces toughness but contribute to dissipate the ballistic impact energy by means of fiber/matrix delamination process.

Conflicts of interest

The authors declare no conflicts of interest.

Acknowledgments

The authors of the present work thank the Brazilian supporting agencies CAPES for the funding; to the Laboratory of Materials of the Brazilian Army Technology Center (CTEx) for the FTIR measurements; and the Brazilian Army Assessment Center (CAEx) for performing the ballistic tests.

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Paper was part of technical contributions presented in the events part of the ABM Week 2017, October 2nd to 6th, 2017, São Paulo, SP, Brazil.

Copyright © 2018. Brazilian Metallurgical, Materials and Mining Association
Journal of Materials Research and Technology

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