Bioinspiration & Biomimetics

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Bioinspired hierarchical impact tolerant materials

To cite this article before publication: Susana Estrada et al 2020 Bioinspir. Biomim. in press https://doi.org/10.1088/1748-3190/ab8e9a

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Page 1 of 26 AUTHOR SUBMITTED MANUSCRIPT - BB-102158.R1

IOP Publishing Journal Title

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Bioinspired hierarchical impact

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19 Susana Estrada a, Juan Camilo Múnera a, Javier Hernández b, Mauricio Arroyave b,
20 Dwayne Arola cd, and Alex Ossa a*

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25 a Department of Production Engineering, Universidad EAFIT, Medellín, Colombia
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c Department of Materials Science and Engineering, University of Washington, Seattle, USA

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34 * Corresponding Author: eossa@eafit.edu.co
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38 Received xxxxxx
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40 Accepted for publication xxxxxx
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48 Abstract
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51 The quest for new light-weight materials with superior mechanical properties is a goal of materials scientists and
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53 engineers worldwide. A promising route in this pursuit is drawing inspiration from Nature to design and develop
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55 materials with enhanced properties. By emulating the graded mineral content and hierarchical structure of fish scales
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57 of the Arapaima Gigas from the nano to macro scales, we were able to develop bioinspired laminated composites
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59 with improved impact resistance. Activated by the addition of nano-particles of Al2O3 and nano-layers of TiN to a
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6 thermoplastic fiber substrate, new energy dissipation mechanisms operating at the nanoscale enhanced the energy
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8 absorption and stiffness of the bioinspired material. Remarkably, the newly developed materials are easily

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13 Keywords: Bioinspiration; hierarchical structure; nano-reinforcement, energy absorption, nano-mineralization.

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20 1. Introduction

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23 Materials applications that demand resistance to impact loads, such as those present in aerospace structures, body
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25 armor, sports equipment, etc., fuel the constant search for stronger, tougher and increasingly lightweight materials.
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The ability to absorb impact energy requires strength, which is usually associated with materials that exhibit high

density and brittleness. Similarly, impact tolerant applications require deformation ability to absorb and dissipate
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31 impact energy. These combination of properties (i.e., high strength and the capacity for large deformation) are
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33 typically challenging for engineering materials; however, can be widely found in biological materials [1–6]. After
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millions of years of evolution, biological materials have inspired engineers to develop novel materials with
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enhanced properties comprising a field of study known as biomimetics [7]. Bone, mollusk shells, osteoderms and
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40 fish scales are typical natural examples that have inspired engineers to develop new impact tolerant biomimetic
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42 materials with extraordinary properties [8-19].
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45 Despite differences in structure and performance, biological materials share a commonality: they are made up
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47 of biopolymers and biominerals, which are organized hierarchically from the atomic to the macroscale [2,3]. This
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49 structure is key to a combination of energy dissipation mechanisms that are activated over multiple orders of length
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scales [5]. Therefore, a recurring characteristic among impact tolerant bioinspired systems is the introduction of
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53 hierarchy at the micro and macroscales. Synthetic materials can be developed to achieve a hierarchical structure
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55 [20]. However, while biological materials generally exhibit between four and eight levels of hierarchy [1], man-
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3 To exploit the possibilities of bioinspired hierarchical design Grunenfelder et al. [12] manufactured carbon fiber
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5 reinforced epoxy composite laminates with a helicoidal arrangement of unidirectional plies, similar to the Bouligand
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structure of crustacean exoskeletons. Their laminates exhibited three orders of hierarchy through: i) carbon fibers,
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ii) the module of unidirectional fibers plied in a helicoidal pattern, and iii) the repetition of that module along the
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12 cross-section of the laminate thickness. When compared to unidirectional and quasi-isotropic laminates, the
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14 helicoidal laminates showed a reduction in through-thickness damage. Cracks in carbon-epoxy composites extend
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16 preferentially through the matrix, rather than severing the strong fibers. The Bouligand-like stacking arrangement
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18 promoted complex patterns of crack propagation, preventing catastrophic crack growth [12]. Other material systems
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20 emulating the protection systems of fish scales and mollusks have achieved two to three orders of hierarchy through:

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22 i) the repeating stiff units (synthetic scale or nacre brick), ii) the arrangement of stiff units emulating overlapping
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24 scales or nacre brick-and-mortar structure, and iii) these arrangements attached to a polymeric substrate
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[9,13,14,21]. In particular, Gu et al.[14] fabricated a cross lamellar structure using additive manufacturing, which

emulated the architecture of a conch shell. The addition of a second level of lamellar hierarchy increased the impact
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31 performance by 70% compared with a single addition of hierarchy level, and by 85% compared with the stiff
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33 material of the composite. Collectively, the results of these studies show that introducing additional orders of
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35 structural hierarchy can significantly improve the energy-absorbing capability of synthetic materials. While these
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37 studies help establish the promise of bioinspired concepts in materials development, the resulting arrangements
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39 achieved mostly by laser engraving and 3D printing have limited levels of hierarchy. This limitation, however,
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41 could be surpassed through the use of nanotechnology.
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44 Besides energy dissipation, flexibility and light-weight are required characteristics in personal protection
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46 applications [6]. To this end, elasmoid scales emerge as proper natural models since they are light-weight
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48 mineralized units that enable mobility to fish while providing strong protection against predators. In particular,
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Arapaima gigas scales can provide protection against highly demanding predatory threats such as piranha attacks
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[22]. The structure of these scales consists of multiple layers of collagen fibers arranged in helicoidal arrangements
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55 with increased mineral content towards the outermost layers of the scale [22–27]. This work hypothesizes that this
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3 graded mineralization supported by a hierarchical structure is key to obtain enhanced protection without a significant
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5 increment of weight.
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8 Using Arapaima gigas fish scales as inspiration, here we incorporate nano-scale mineral reinforcements (e.g.,

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10 Al2O3 and TiN) into laminar organic fibrous composites (UHMWPE) to develop a system that emulates the natural
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mineralization present in the scales. New orders of hierarchy are introduced within the structure of this impact
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tolerant system, which triggers new energy dissipation mechanisms at the nanoscale. Using this strategy, we
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17 developed a new generation of composites with five orders of hierarchy, which renders a considerable enhancement
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19 of energy absorption without a significant increase in weight.
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22 2. Elasmoid Fish Scales
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25 Elasmoid scales are flexible, lightweight, impact tolerant materials that help protect a wide variety of fish against
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predatory threats. They are mineralized units that are partially embedded within a highly flexible tissue backing

layer, and overlap one another to maximize the capacity for protection [27–32]. Like other biological structural
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31 materials, elasmoid scales possess a hierarchical structure. They are comprised of a combination of type I collagen
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fibers and apatite, which are the fundamental constitutive elements among other natural mineralized systems [4].
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The role of fibers and reinforcements in fish scale composites is the opposite of most mineralized biological tissues
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38 (e. g. dentin and bone), here the collagen fibers are the organic portion and the matrix (i.e. minerals) are the
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40 reinforcement. Depending on the degree of mineralization, elasmoid scales can be divided into two different layers
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42 (Figure 1a): a highly mineralized rough external layer termed Limiting Layer (LL), consisting of a mineral matrix
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44 with randomly dispersed thin collagen fibers (30 - 50 nm in diameter), and a basal plate commonly regarded as the
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46 elasmodine, which consist of densely packed layers of unidirectional collagen fibrils (100 - 160 nm in diameter).
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48 Depending on the mineral distribution, the elasmodine can be further divided into the External (EE) and Internal
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50 Elasmodine (IE). The EE is more highly mineralized due to an increased reinforcement of apatite platelets [33].
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Collagen fibrils of the elasmodine are packed into larger fibers, which are aligned and assembled into individual
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unidirectional plies (or lamellae). These plies are stacked with a helicoidal arrangement commonly known as a
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Bouligand structure [22].
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3 Interestingly, the Bouligand structure serves a critical role in the mechanical behavior of this material system by
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5 enhancing the ductility and toughness of scales [34]. Furthermore, the hierarchical structure facilitates the
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dissipation of energy across different length scale levels [22,35]. At the macroscale (> 1 mm), the outer layer (LL)
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dissipates energy through mechanisms of brittle fracture, while the basal fibrous structure undergoes a high degree
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12 of deformation before failure [36]. At the micro-scale (1 μm to 1 mm), the Bouligand arrangement facilitates a
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14 reorientation of the lamellae in response to the loading direction. Under in-plane tensile loads, deformation occurs
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16 through a combination of stretching and interfacial sliding mechanisms [33,34]. And at the nano-scale (1 nm - 1μm),
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18 the collagen fibrils straighten, rotate, stretch, and eventually undergo fracture, a process that dissipates substantial
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20 energy. This process is accompanied by the resistance to sliding caused by the interfibrillar nanoscopic mineral

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22 platelets of apatite. As such, this behavior is highly dependent on the mineral content.
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25 In mineralized tissues consisting of moderate mineral content, the collagen fibrils uncoil first and then increase
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their stiffness due to the stress transfer among the mineral platelets present [5]. At the atomic scale (< 1 nm), the

collagen molecules dissipate energy by uncoiling and through breaking and reforming of hydrogen bonds between
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molecular chains [5]. This interplay between the different energy dissipation mechanisms allows efficient and light-
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weight protection against predation; however, these mechanisms are highly affected by the hydration level of the
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36 scales. Indeed, the stiffness, strength and toughness of the scales have shown to be highly dependent on water
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38 content [25,37].
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41 Arapaima fish possess elasmoid scales, providing protection against piranha attacks. The Arapaima gigas is a
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43 species of arapaima that is native to the Amazon River basin of South America and is among the world’s largest
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45 freshwater fish. It is covered by scales with lengths between 5 - 7 cm and average widths of ~4 cm [25]. The LL
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47 of its scales is about 600 μm in thickness, while the elasmodine can be as thick as 1000 μm. Unlike most other fish,
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49 the lamellae of the elasmodine are arranged with a stacking sequence of approximately 0°/90°, which is equivalent
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to a cross-ply orthogonal laminate structure [33]. The ply thickness ranges from 30 to 60 μm [24,33]. The
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of fibrils of smaller diameter (~100 nm) [24]. The mineral structure within the layer of these scales was recently
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3 detailed and consists of platelets with a thickness of ~50 nm and diameters of ~500 nm [22,25]. Overall, the
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5 microstructure of the Arapaima gigas scales exhibits six orders of hierarchy (Figure 1a).
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Here we propose a material system inspired by the structure of Arapaima gigas scales. The foundation is a
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14 laminated composite of unidirectional plies of ultra-high molecular weight polyethylene (UHMWPE) fibers within
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16 a rubber-based matrix. The laminate possesses a cross-ply arrangement similar to the 0°/90° ply configuration of
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18 Arapaima scales [33]. These composites are widely used in the armor industry under brands such as Spectra® and
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20 Dyneema®. Analogous to the mineral reinforcement of scales, we introduce nano-scale mineral reinforcements

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22 between the exterior-most layers of the laminate to increase the strength and energy absorption, without significantly
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24 increasing the weight of the material. The structure of this newly constructed material exhibits principles that are
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consistent with those of the Arapaima gigas scales (Figure 1b).

The laminates were comprised of eight layers of Dyneema® HB50, consolidated into a plate by thermo-pressing.
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31 Selected properties of Dyneema® HB50 and Dyneema® fibers are shown in Table 1. Each layer of Dyneema®
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HB50 consisted of four plies of unidirectional fibers cross-plied at 90° to each other. The laminates were pressed at
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100 bar at a temperature of 125 °C for 35 minutes and then removed from pressure once the temperature was below
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38 60°C, following material’s supplier recommendations. For repetition, 5 samples of each design were fabricated and
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40 tested.
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43 Table 1 Selected properties of Dyneema HB50 and Dyneema fibers. Information obtained from suppliers’
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data sheets [38,39].
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47 HB50 Dyneema fibers
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49 Areal density (g/m2) Axial tensile modulus (GPa) Transverse modulus (GPa) Elongation at break (%)
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55 To compare the mechanical performance and structural differences of the bioinspired materials, three different
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3 laminates with Aluminium Oxide (Al2O3) nanoparticles, and iii) Reinforced laminates with Titanium Nitride (TiN)
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5 nanocoatings. Each sample consisted of a disc-shaped plate with a 200 mm diameter and ~2 mm of thickness (see
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Figure 2a).
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10 Two different manufacturing strategies were adopted to introduce the nano reinforcements into the laminates. A
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nano-spray process was used to deposit spherical nano-particles between the laminate plies, while Radio Frequency
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Magnetron Sputtering was used to introduce the nano-coatings.
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3.1 Aluminium Oxide reinforced laminates
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21 The nano-spray process for introducing the Al2O3 nanoparticles reinforcement consisted of spraying three of the
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23 eight layers of the laminate with a colloidal suspension. These reinforced layers were stacked successively towards
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25 the external face of the laminate, combined with five non-reinforced layers, followed by thermo-pressing (see Figure
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2b). After thermo-pressing, the stacking sequence of the laminate exhibited two different regions along the cross-

section, which resembled the elasmodine structure of Arapaima scales. Specifically, the laminate consisted of a
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31 mineralized external region (i.e. EE), and a non-mineralized basal region (i.e. IE) [26].
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34 In the manufacture of Al2O3 reinforced laminates, liquid polyurethane (PU) was mixed with Al2O3 nanoparticles
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36 (~500 nm in diameter, MSESUPPLIES). The mixture was prepared in the following weight proportions: PU 41.7%,
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38 solvent 21%, catalyst 26.9% and Al2O3 particles 10.4%. The mixture of nanoparticles was applied by using a paint
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gun in two layers of homogeneous thickness, reaching approximately 500 m. Three of the eight layers forming the
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43 bioinspired laminate were coated with this mixture between 1 and 10 minutes after adding the catalyst. The coated
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45 layers were left to dry for 24 hours at room temperature before consolidating into a laminate through thermo-
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50 3.2 Titanium Nitride reinforced laminates
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53 Titanium Nitride (TiN) layers were produced by a high vacuum Radio Frequency Magnetron Sputtering
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55 equipment (H2 Intecovamex) configured with a cubic stainless-steel vacuum chamber (300x300x300 mm). The
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3 sputtering targets. The sputtering process was developed at 5 mTorr of pressure in atmosphere of Argon (90%) and
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5 Nitrogen (10%) during 70 minutes at 150 Watts of Radio Frequency Power.
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8 To manufacture the TiN reinforced laminates the three outermost layers of the composite were coated before

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10 thermo-pressing with a thin layer of TiN (~300 nm in thickness) using radio frequency magnetron sputtering.
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Thereafter, the reinforced and unreinforced layers were stacked and thermo-pressed with the same two-region
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configuration described for Al2O3 reinforced laminates (see figure 2b).
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3.3 Impact tests
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23 equipment with a loading rate of 2 m/s. A custom clamping was used to hold the laminates in place during impact,
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25 in which laminates were fixed through bolts, leaving 100 mm of free space for the laminate to deform. The clamping
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device was made of hardened steel (Figure 3a). The steel striker was made with a conical-spherical shape to allow

a considerable energy transfer to the laminates tested (Figure 3a). The impact results were evaluated at 3 mm of
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33 was taken to avoid any slip of the samples during testing by using sandpaper between samples and clamping device.
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36 A typical load-deflection impact response is shown in Figure 3b. Mechanical strength was considered here as the
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38 maximum impact load at 3 mm of deflection, stiffness was defined as the ratio between load and deflection at 3
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40 mm of deflection, and the energy absorbed was defined as the area under the load-deflection curve once achieved 3
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mm of deflection, as shown in Figure 3b. The choice of 3 mm of displacement to evaluate the energy absorbed by
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45 the tested samples ensured to have a constant speed of the striker up to this point. Soon after 3 mm the striker started
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47 to decelerate, reducing the impact speed. Further, after approximately 1 mm of displacement the deformation of the
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49 samples showed permanent deformation (plasticity), which was important as a measure of the energy absorbed by
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the samples. It is worth noting that none of the samples tested reached failure.
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3 Small sections of the bioinspired laminates (about 2 mm in thickness) were embedded in cold-cured epoxy resin
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5 in order to inspect their microscopic characteristics. These sections were further ground with sandpaper with
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successive grit sizes of 120, 220,400, 600, 1000 and 1200, until having final thicknesses of the laminates of about
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200 μm. Further polishing by means of red felt polishing cloths was performed using diamond particles of 6 μm, 3
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12 μm, and 1 μm in size. Optical microscopy was then carried out on the samples using transmitted light by using an
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14 optical microscope (Axiovert 40 MAT, Carl Zeiss, NY). The same samples were further used for atomic force
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16 microscopy analysis. Images were obtained at standard conditions (T = 20 °C and R.H. = 50%) using an atomic
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18 force microscope (AFM; XE7, Park Systems Inc.). Commercial silicon AFM tips with diamond-like carbon (DLC)
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20 coating (TAP150, Budget Sensors) having a nominal stiffness k = 5 N/m and tip radius R = 25 nm were used in the

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25 4. Results and discussion
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One of the main differences between the two typologies of reinforced laminates manufactured was the continuity
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of the reinforcing phase. While the Al2O3 particles consisted of discrete particles dispersed in a polyurethane matrix,
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35 reinforcement of Al2O3 is shown between the fiber plies in Figure 4a, and the continuous reinforcement of TiN is
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37 shown as a monolithic layer between fiber plies in Figure 4d. Both of the reinforced laminate configurations possess
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39 a five-order hierarchical structure as shown in Figure 1b.
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42 4.1 Microscopy results
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45 The microstructure of the bioinspired laminates is shown in Figures 4b and 4e, with light and dark alternating
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47 regions representing layers of fibers arranged in a cross-ply configuration. The fibers oriented perpendicular to the
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49 observer can be seen in the lighter areas of the image, where circular individual UHMWPE fibers with a diameter
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of ~17 μm can be seen. The dark area towards the center of the images corresponds to one nano-mineralized layer.
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53 Figure 4c shows the structure of Al2O3 particles with diameters of ~500 nm dispersed in the polyurethane matrix,
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while Figure 4f shows the TiN nano-layer with a thickness of ~300 nm.
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3 4.2 Impact results
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6 Results of the impact tests show that both the Al2O3 and TiN nano-scale reinforcements increased the impact
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8 resistance of the bioinspired composites (Figure 5). While the unreinforced composites reached an average

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maximum load of approximately 640 N, the bioinspired composite reinforced with Al2O3 nano-particles reached an
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13 average maximum load of 730 N, representing over 14% increase in impact load. On the other hand, the nano-

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15 reinforced TiN composites achieved an average maximum load of 760 N, an increase of approximately 18% when
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17 compared with the unreinforced material.
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20 The differences in resistance to transverse deformation of the reinforced composites under impact loading are

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22 also reflected in their ability to absorb impact energy. Figure 6 shows the absorbed energy profiles for the materials,
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24 with respect to their stiffness. While the unreinforced material reached an average absorbed energy of 0.80 J with
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26 stiffness of roughly 305 N/mm, the laminate reinforced with Al2O3 reached an average absorbed energy of 0.96 J
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with a stiffness of 335 N/mm. That represents a 20% increase in absorbed energy with a 9% increment of stiffness
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energy with a stiffness of 355 N/mm. When compared to the unreinforced materials, that represents a 23% increase
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in energy absorbed and an 18% increment in stiffness. In demanding impact loading applications like aerospace,
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37 body armor and sports equipment, energy enhancements of these levels can render equivalent weight reductions.
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39 The statistical analyses showed that the differences in response between the three different composites were
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41 significant (p ≤ 0.05). The post-hoc analysis showed that there were significant differences between the unreinforced
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43 and bioinspired composites, but no significant difference in performance between the Al 2O3 and TiN reinforced
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Table 2 Dynamic testing results for reinforced and unreinforced samples, showing the mean (µ), standard
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each sample configuration under impacts at 2 ms-1. For repetition, five samples for each configuration
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Load (N) Energy (mJ) Stiffness (N/mm)
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7 Unreinforced 639,7 48,5 8% 0,796 0,049 6% 305,3 16,2 5%
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9 Reinforced with Al2O3 729,6 49,5 7% 0,956 0,029 3% 333,9 16,5 5%
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Reinforced with TiN 756,7 32,1 4% 0,982 0,032 3% 359,1 10,7 3%
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15 4.3 Discussion
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18 The introduction of hierarchical structures has recently been used to obtain extraordinary properties in synthetic
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20 materials [14]. However, it is presently impossible to introduce hierarchy at length scales below the micro and

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22 macro scales by using technologies such as additive manufacturing or laser engraving. As such, nanotechnology
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24 appears to be the most viable option for introducing new levels of hierarchy in the development of synthetic
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materials. The bioinspired composites fabricated in this study achieve five orders of hierarchy: i) the UHMWPE

fibers; ii) a ply of unidirectional fibers; iii) a laminated layer of four cross-ply unidirectional plies; iv) three nano
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mineralized layers; and finally v) the bioinspired laminate with “graded” mineralization, similar to the EE and IE
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33 of fish scales (Figure 1). A sixth order of hierarchy could be achieved if the molecules of the polyethylene fibers
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35 were considered at the atomic scale.
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38 Fish scales exhibit an interesting distribution of mineral content across their thickness. Arola et al. studied the
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40 mineral content of the outermost layer of the scale (LL) in different fish species [36]. Regardless of species, the
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42 mineral content is maximum on the exterior surface of the LL, and then decreases to the LL/EE interface. The
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44 mineral content remains nearly constant in the EE and then undergoes an abrupt decrease to nearly zero in the IE
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46 [52]. In essence, the IE consists of plies of unidirectional collagen fibers without any mineral content. For the
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48 Arapaima scales, the volume fraction of apatite decreases from 60% to 40% over the thickness of the LL, remains
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50 nearly constant in the EE and then reduces to 0% within IE [36]. Similarly, our bioinspired materials have highest
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mineral content towards the external layers of the composite due to the TiN and Al2O3 reinforcement. The volume
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3 The mechanical properties of the bioinspired laminates are highly dependent on the properties of the
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5 reinforcement. The Young’s modulus of Al2O3 and TiN is approximately 300 GPa and 600 GPa, respectively. Apart
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from Young’s moduli, the difference in morphology between the two types of reinforcements is also important to
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the mechanical responses. The Al2O3 particles were dispersed within a rubber-based matrix, serving as
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12 discontinuous reinforcements, while the TiN coatings formed a continuous layer of reinforcement, which is in direct
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14 contact with the UHMWPE fibers. The later configuration enhanced stress transfer between the reinforcements and
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16 fibers. It is worth noting that our bioinspired laminates have a minimal mineral content of approximately 1%, which
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18 is substantially lower than that of the Arapaima scales (40%). Achieving a mineral content of 40% in the external
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20 layers of the bioinspired laminates would double their weight in comparison to those without reinforcement. Clearly

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22 this would be problematic for industrial applications in aerospace and sports where weight reduction is always a
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24 priority.
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The hierarchical approach involving the introduction of nano-scale reinforcements enabled the fabrication of

high-strength composites with low-density. Both manners of reinforcement significantly increased the stiffness and
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energy absorption with minimal increase in weight (Figure 7). While the addition of Al2O3 reinforcements was
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accompanied by a 2.5% increase in weight, the TiN reinforcement caused an increase of approximately 0.15%. Both
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36 forms of the nano-scale reinforcements served as extremely thin layers of stiff reinforcements with no significant
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38 increase in weight. Nevertheless, both forms of reinforcement interacted with the UHMWPE fibers (Figure 6) and
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40 plies in a manner that improved the overall mechanical performance of the material.
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43 A recent study concerning the deformation mechanisms of unreinforced UHMWPE composites under transverse
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45 impact reported that failure occurs in a progressive manner. Ply fracture begins at the interface between the striker
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47 and the composite and propagates to the rear of the laminate [40]. The failure process occurs through tensile failure
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49 of the plies by an indirect tension mechanism, wherein the transverse compression stresses generate tensile stresses
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in-plane due to a mismatch in the properties between the alternating 0° and 90° plies. This process is accompanied
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53 by fiber sliding, which is evidenced by outward extruded fibers found in the cross-section of the impacted
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composites. This interaction occurs at both the ply and fiber levels, which ranges across three decades of length
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58 scale (1 μm to 1 mm). However, when nano-reinforcements are integrated into the laminates, interfacial friction
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3 between the plies limits the sliding and stretching of fibers, thereby improving the coupling between fibers. Thus,
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5 in the development of tensile stresses within the fibers through indirect tension, the increased friction spreads fiber
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recruitment in supporting the mechanical load. That process ultimately allows the stress to be distributed over wider
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areas, thus reducing damage. Certainly, the increased friction between fibers is a complementary mechanism of
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12 energy dissipation facilitated by the nano-scale reinforcements, which manifests as an increase in the mechanical
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14 performance of the reinforced materials at the macro scale.
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17 Similar phenomena have been found in both natural and artificial systems. For instance, in fish scales,
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19 dehydration causes resistance to sliding between collagen fibers, which increases the elastic modulus and strength
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21 of dehydrated scales [25,37]. The stiffening mechanisms associated with this phenomenon have already been
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23 reported by Jiang et al [41]. Similarly, in synthetic systems such as liquid armor, the high-performance fabrics
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25 increase their mechanical properties via resistance to fiber sliding promoted by the introduction of Shear Thickening
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Fluids (STF) [42]. STF are dense colloidal suspensions that can exhibit an abrupt increase in the viscosity with an

adequate increase in shear rate or applied stresses. When used in protective applications, STF improve the
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performance of the fabrics, but their major contribution is not derived from their shear thickening behavior. Rather,
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the solid particles increase the friction between fibers, which ultimately causes spreading of the load over wider
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36 areas [43–45]. Particle volume fraction and particle size are some of the characteristics that affect the performance
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38 of STFs. These factors could also affect our bioinspired materials. The lower limit of the particle volume fraction
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40 for the thickening behavior of colloidal suspensions depends on the material properties. It has been reported that the
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42 thickening behavior of STF is generally activated at a particle volume fraction exceeding 0.5 [43]. In contrast, the
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44 volume fraction of Al2O3 particles in the present work was about 0.01, which is significantly lower than that stated
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46 to trigger the thickening behavior of the STF. Although impact tests show that this minimum volume fraction (0.01)
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48 can improve the energy absorption and stiffness of bioinspired laminates, future work investigating the effect of this
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volume fraction on the properties of the laminate is warranted, as this may open new opportunities for optimization.
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53 An analysis of the relations between fibers and reinforcements for the natural and bioinspired materials show
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important similarities. The collagen fibers present in Arapaima gigas scales have a diameter of 1 μm with a mineral
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58 reinforcement consisting of platelets with a thickness of 50 nm [22,25]. On the other hand, the fibers present in our
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3 bioinspired laminates have a diameter of 17 μm accompanied by reinforcements of different sizes depending on the
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5 nano-mineralization strategy. The Al2O3 particles were approximately 500 nm diameter, and the TiN reinforced
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layer thicknesses were approximately 300 nm. The reinforcement/fiber (RF) ratio, defined as the ratio between
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particle diameter (or coating thickness), and fiber diameter, shows that the Arapaima scales exhibit an RF ratio of
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12 0.05. That value for the Al2O3 and TiN reinforced laminates is ~0.03 and ~0.02, respectively. Future studies that
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14 explore the importance of this ratio between the constituent units of bioinspired laminates and their effect on internal
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16 friction could lead to further improvements on mechanical properties.
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19 Previous studies have shown that the stacking sequence of unidirectional fiber laminates can significantly affect
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21 the mechanical behavior of bioinspired composites. Hazzard et al. [46] showed that lamination patterns such as
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23 rotational, helicoidal or quasi-isotropic configurations can achieve superior mechanical behavior of thin Dyneema®
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25 panels under low-velocity impacts when compared with cross-ply arrangements. They suggested that the
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deformation mechanisms exhibited by cross-ply laminates were dominated by substantial in-plane shear with

limited load transfer from primary fibers, which is an energy dissipation mechanism exhibited at the microscale (1
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μm to 1 mm). The load transfer between fibers could be maximized by introducing nano-scale reinforcements
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following the strategy applied here. Considering that the laminates in this work were inspired by the cross-ply
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36 patterns in Arapaima scales [33], further work could consider the combined effect of nano reinforcements and
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38 varying lamination patterns on the mechanical properties of the materials.
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41 One of the primary aims of this work was to develop strategies for manufacturing hierarchical low weight energy
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43 absorption materials that could be easily adopted in the industry. The effect of the manufacturing process on energy
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45 and weight variations can be analyzed if a figure of merit relating energy absorbed, density and cost is used, as
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47 shown in Figure 7. Here, an increased value will represent low weight and low cost with increased energy
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49 absorption. According to this ranking, the addition of nanoparticles stands out as a viable option for industrial
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scaling. Radio frequency magnetron sputtering increases the cost about 17 times in comparison to the unreinforced
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53 material, whereas the production cost of the nanoparticle reinforcements results in just about 1.3% increase. Given
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that no significant differences were found in the impact resistance between the two bioinspired materials,
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58 introducing reinforcements by nano-spray coating is considered the best option to be industrially scaled.
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3 5. Concluding remarks
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This work proposed a hierarchical approach to mimic the graded mineralization exhibited by Arapaima scales,
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9 with a variation in the level of mineralization from the top to the bottom of elasmodine. By using two different nano
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11 mineralization strategies (i. e., Al2O3 nanoparticles and TiN nanocoatings) into a laminar organic fibrous composite,
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13 three different sample typologies were obtained: i) unreinforced, ii) reinforced with Al2O3, and iii) reinforced with

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15 TiN. Dynamic tests revealed that the impact resistance of the reinforced materials was increased significantly with
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17 respect to the non-reinforced materials, with a 20% to 23% increase in absorbed energy for materials reinforced
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19 with Al2O3 and TiN respectively. Remarkably, this enhancement in impact performance was obtained with a
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21 negligible increase in the weight (i. e., less than 2,5 % in Al2O3-reinfoced materials and barely 0,15 % in TiN-
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23 reinforced materials). The microscopy analysis suggested that the enhanced impact performance resulted from a
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new energy dissipation mechanism at the nanoscale. This mechanism involves increased friction between the fibrous
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layers of the laminate through interfacial nano-scale reinforcements. Remarkably, the Al2O3-based mineralization

30 strategy can be industrially scaled up due to their low added costs. Therefore, this strategy for developing bioinspired
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32 hierarchical materials may bring the benefits of biomimetics to the next generation of light-weight, cost-efficient,
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34 impact-tolerant, high-performance protective materials.
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40 Acknowledgements
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The authors like to express their gratitude to Universidad EAFIT for their financial support.
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46 References
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40 macroscale (100 m) to the atomic scale (10-9 m). Coloring represents a higher degree of mineralization. (a)
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42 Hierarchical structure of Arapaima scales, shown from top to bottom: Arapaima gigas fish, an elasmoid
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scale, a cross-section of the scale, collagen fibers arranged in a cross-ply configuration, a ply of
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45 unidirectional fibers, a mineralized collagen fiber with colored dots representing hydroxyapatite, a
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47 mineralized collagen fibril with colored dots representing hydroxyapatite, and the tropocollagen structure
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49 of the collagen molecule. (b) Hierarchical structure of bioinspired composites, showing from top to
50 bottom: a plate of bioinspired material, the cross-section of the laminate showing graded mineralization
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52 (R, Reinforced and UR, Un-reinforced), UHMWPE fibers arranged in a cross-ply configuration with a
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54 nano-mineralized layer, two plies of UHMWPE fibers reinforced with a layer of nano-mineralization, a
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39 mineralization. The three outermost layers of Dyneema® HB50 were reinforced with minerals (i.e., Al2O3
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32 diameter of ~500nm, scale bar corresponds to 1 μm, Al2O3 nanoparticles are pointed by arrows; (d) scheme
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34 of cross-ply fibers reinforced with Titanium Nitride (TiN); (e) cross-section of a laminate reinforced with
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TiN observed through optical microscopy using transmitted light, scale bar corresponds to 100 μm; (f)
37 AFM non-contact phase image of a laminate reinforced with TiN showing a TiN layer of ~300 nm, scale
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39 bar corresponds to 1 μm, TiN layer is pointed by an arrow.
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34 Figure 5. Load versus deflection response from the impact tests performed on the bioinspired and
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36 unreinforced materials. Colored areas with transparency represent the standard deviation of the measured
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34 Figure 6. Absorbed energy versus stiffness of the bioinspired and unreinforced materials. The inset shows
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the percentage of energy increase of the reinforced materials (Al2O3 and TiN) in comparison to the
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Figure 7. Figure of merit representing materials performance accounting for energy absorption, weight
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40 measurements for each type of material.
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