Article-Bioinspired “Wooden Armor” based on Micro-nano Lignocellulose

with Bouligand Structure

Reprinted with permission from (Bioinspired Construction of Micronano Lignocellulose into an Impact Resistance “Wooden
Armor” With Bouligand Structure, : Yipeng Chen, Baokang Dang, Jinzhou Fu, et al, ACS Nano, May 1, 2022,
https://doi.org/10.1021/acsnano.1c10725) Copyright © 2022, American Chemical Society

Recently, the acts of terrorism and worldwide violent conflicts like what is happening today between Russia and Ukraine or
in many other countries, namely, Syria, Palestine, Azerbaijan, Armenia, Afghanistan Taiwan, China and so on are rising at an
unprecedented scale, which is leading to grievous bodily injury or even loss of human lives on a very large scale. In such a
life and death situation there is an acute need to design and develop lightweight protective armour with high mechanical
strength along with superior performance and ability to withstand dynamic impact without causing any major structural
damage.

Presently, man-made impact-resistant materials with exceptional mechanical performance, including Rolled homogeneous
armour (RHA) steel, aluminium alloys, titanium base alloys, impact-resistant glass, ceramics (e. g., SiC, Al2O3, B4C, ceramic
matrix composites (CMCs)), polymer matrix composites etc. are being widely used for military applications such as bullet
proof jackets, vehicle safety protection, bunkers, naval and helicopter safety protection and so on. However, they are
heavy; expensive as they are made by energy intensive processes; moreover, in the case of ceramics there is a catastrophic
failure due to their inherent brittleness and poor impact toughness while CMCs are fabricated by sophisticated long-time
processing making them unduly cost-prohibitive. Although, metallic based alloys show excellent impact toughness but their
high density precludes their widespread applications.

In view of the above, there is an urgent need to develop lightweight armour with an improved flexibility without degrading
it’s ballistic and blast protection capability. Biological materials and assemblies found in nature possessing hierarchical
microstructures with superb mechanical properties provides an inspiration to design lightweight, flexible and tough body
armours. A few examples of biological composite structures are ( Inspiration from Nature's body armours – A review of
biological and bioinspired composites) Nacre: Staggered multi-layer polygonal tablet’s structure; Conch: Cross-lamellar
ceramic armour system; Fish scales: Flexible multi-layer armour system; Crustacean (crab) exoskeleton: Helicoidal fibre
reinforced structural configuration; Cortical (compact) bone: multi-layer column-like structure with collagen fibres. Recent
studies suggest that fish skins, nacre, turtle shells bird beaks, horns, shark teeth, and horse hooves have shown fairly good
impact-resistant properties (Biomimetic armour design strategies for additive manufacturing: A review).

One of the interesting examples is conch shell, in this report the authors devised a novel approach (hierarchically
enhanced impact resistance of bioinspired composites) elaborating the progress in creating a biomimetic conch shell
prototype, using additive manufacturing. The prototypes were able to achieve improvements in impact resistance on
demand by recreating the complex crisscrossed lamellar architecture as seen in natural conch shells.
The most interesting example (Mechanical adaptability of the Bouligand-type structure in natural dermal armour) that
pertains to the present article is the Bouligand type of structure found in Arapaima gigas, which is a fresh water fish found
in the Amazon Basin that is able to resist the ferocious attack by piranhas through the strength and toughness of their
scales, which act as natural dermal armour. Furthermore, it can also be described as a layered and rotated microstructure
resembling plywood, which is frequently found in naturally designed materials. It consists of multiple lamellae, or layers,
each one composed of aligned fibres. Adjacent lamellae are progressively rotated with respect to their neighbours (Sur une
architecture torsadée répandue dans de nombreuses cuticules d'Arthropodes).

Natural wood (Processing bulk natural wood into a high-performance structural material) is a low-cost and abundantly
available material and has been used since a few thousand years as a structural load bearing material for buildings, marine
industry and furnishing. However, the mechanical performance of natural wood (its strength and toughness) is not up to
the mark for many advanced engineering structures and applications. Natural wood available in a raw state could be pre-
treated with steam, heat, ammonia, free radical initiation or acid catalysis or cold rolling followed by densification has led
to the enhanced mechanical performance of natural wood (Processing bulk natural wood into a high-performance
structural material}. However, the existing methods result in incomplete densification and lacking in dimensional stability,
particularly in response to humid environments, and wood treated in these ways is susceptible to swelling and loses its
strength. Moreover, the current approaches lead to inadequate densification and reduction in toughness.

Lignocellulose is indeed a complicated natural biomaterial at nano- and microscales. It is mostly existing in the form of
plant materials such as such trees, bushes and grass, is one of the most abundant organic materials in natural world
(Lignocellulosic Biomass: Understanding Recalcitrance and Predicting Hydrolysis).

Lignocellulosic materials are having three main structural polymer components: cellulose, hemicelluloses, and lignin. Out of
which, cellulose and hemicellulose are carbohydrate polymers, while the lignin is a non-carbohydrate phenolic polymer
that binds to cellulose fibres to harden and strengthened the plant cell walls. These three are radically different chemically
and are interconnected in a very complex fashion. Majority of the densified wood comprises well aligned cellulose
nanofibers, which to a great extent enhance hydrogen bond formation among neighbouring nanofibers( Processing bulk
natural wood into a high-performance structural material). In the plant cell wall, hemicellulose is linked to cellulose by
hydrogen bond, and to lignin by covalent bonds forming lignin-carbohydrate complexes (LCC). These innumerable
hydrogen bonds impart the materials with great strength, toughness and toughness. Lignocellulose is also composed of
relatively low density parenchyma cells that create a soft foam-like structure, which makes it lightweight in nature.

The present work (Bioinspired Construction of Micronano Lignocellulose into an Impact Resistance
“Wooden Armor” With Bouligand Structure) was aimed at to design and develop bioinspired high strength and high
toughness lignocellulose-based material which is able to utilize as a “wooden armor”. The current processing route
involves laying one-dimensional (1D) lignocellulose nanofibrils in a flexible manner to compose two-dimensional (2D) films
with unidirectional assemblies. Aligned lignocellulose fibers were obtained by brushing-induced assembly, followed by
dipping in shear thickening fluid (by using polyborosiloxane (PBDMS)), and subsequently, efficiently hot-pressing into
macroscopic three-dimensional (3D) body.

Figure 1. (a) Bottom-up assembly strategy of the artificial wooden armor. (b) A large scale 2D films and 3D artificial wooden
armor. Reprinted with permission from ( Bioinspired Construction of Micronano Lignocellulose into an Impact Resistance
“Wooden Armor” With Bouligand Structure, : Yipeng Chen, Baokang Dang, Jinzhou Fu, et al, ACS Nano, May 1, 2022,
https://doi.org/10.1021/acsnano.1c10725) Copyright © 2022, American Chemical Society

The obtained artificial wooden armor had biomimetic flexible-rigid layered Bouligand -like structures on the Pirarucu
(Arapaima gigas) scale.

The impact resistance of synthetic wooden armor is comparable to that of conventional engineering materials (e.g.,
ceramics, glass, and alloys). It is interesting to note, that the density of the wooden armor is approximately half that of the
above-mentioned materials. Additionally, the ease of deformation of the secondary hydrogen bonds in artificial wooden
armor maintains its structural integrity during impact damage, and this in turn, circumvents the catastrophic damage of
glass and ceramics which is attributable to the presence of primary (covalent) bonds. Figure 2 (b) reveals the typical
puncture force−displacement curves of the bioinspired wooden armor, pure wood fiber bulk, and borosilicate glass. The
ultimate puncture force obtained from the force−displacement curves of the initial stage indicates the ability to resist
deformation in elastic regime along with a damage propagation stage. Ei represents the energy associated with the elastic
deformation before crack initiation and Ep represents plastic energy absorbed during crack propagation. As PBDMS is
integrated within the lignocellulose matrix with Bouligand-like structures, the ultimate puncture force increases by ∼13
times-from 119.1 N (pure wood fiber bulk) to 1570.7 N (artificial wooden armor); borosilicate glass exhibits a high strength
but undergoes catastrophic brittle fracture. The strength and resistance to damage of borosilicate glass and pure wood
fiber bulk exhibited poor integrity because of the low Weibull modulus of glass, and hydrogen bond interactions between
cracks in pure wood fiber bulk maintain its macro-morphology. The Ei of the wooden armor was higher than that of the
composite without Bouligand structure, which is ascribed to its soft-rigid dual layered network interactions and a multitude
of deformation mechanisms. The Ep increased significantly when PBDMS was introduced, evidently implying the high
ductility and energy-absorbing capacity of the PBDMS. Therefore, in qualitatively terms, the reinforced performance of the
wooden armor is attributed to the structural features at multiple micro-nanoscale levels where the shear thickening soft
components play a key role. In terms of energy to puncture (Figure 2c), borosilicate glass showed the lowest energy
absorption during puncture, pure wood fiber bulk displayed slightly improved energy absorption due to its ductile nature
and the artificial wooden armor showed greater toughness with large strain resulting in high energy absorption during the
course of its puncture. Wooden armour exhibited improvement in energy to puncture and the impact toughness by 10.4
and 12.4%, respectively, compared with pure wood fiber bulk. To investigate the contribution of the Bouligand-like
structure designs and also to study the relationship of energy to puncture interface adhesives to the energy to puncture,
systematic mechanical tests were conducted. The artificial wood armor, which contains ∼10 wt % PBDMS (optimum
amount) achieved the most desirable energy to puncture (Figure 2(c)) and the ideally appropriate thickness of the film in
this system is ∼65 μm. The mechanical response of the artificial wooden armor was found to be more reproducible than
pure wood fiber bulk and borosilicate glass because the synergistic interface interaction occuring between soft PBDMS and
rigid affixed lignocellulose while restraining the artificial wooden armor, and thereby, the total energy dissipation of
complicated deformation can be increased by Bouligand-like structures.
Author: Yashwant Mahajan, Former Scientist, DRDO/ARC-I
Figure 2(b) Puncture force−displacement curves, (c) Energy to puncture and Charpy impact
toughness of the artificial wooden armor, pure wood fiber bulk, and borosilicate glass,
respectively. Reprinted and adapted with permission from ( Bioinspired Construction of Micronano Lignocellulose into an
Impact Resistance “Wooden Armor” With Bouligand Structure, : Yipeng Chen, Baokang Dang, Jinzhou Fu, et al, ACS Nano,
May 1, 2022, https://doi.org/10.1021/acsnano.1c10725) Copyright © 2022, American Chemical Society

To assess the ballistic impact characteristics of the wooden armor and other competitive materials, the ballistic tests were
performed using a revolver and 9 mm caliber ammunition, with an impact velocity of 214 m/s. MDF The wood armor
maintained superior integrity arising from the complicated helicoidal structure architecture and the high deformability of
the PBDMS interlayers (Figure 3). Although, medium-density fiberboard (MDF)and CRPF are lightweight, they were easily
perforted during ballistic impact test showing poor ballistic resistance performance. Wood was the lightest of the materials
tested; however, it exhibited a relatively low impact resistance. It is also easily fractured under a high loading rate because
of its unidirectionally aligned fibers (not shown in this figure). In general, pure wood fiber bulk, which is slightly denser than
wood, exhibits less impact resistance because of its weaker interlayer interfaces. Borosilicate glass and ceramics are
approximately five times as dense as wood and pure wood fiber bulk, with a higher impact resistance as well. However, the
rupture was catastrophic and accompanied by many small fragments. The NVE 36 metallic alloy exhibits the highest impact
resistance with a relatively high density.
Figure 3: Comparison of specific ballistic energy absorption of the artificial
wooden armor with other common structural materials. The equation inset
is for the specific ballistic energy absorption, where v1 and v2 are the velocities
of the bullet before and after passing through the sample, m is the mass of
bullet, and h and ρ are the thickness and density of the sample, respectively.
Reprinted and adapted with permission from ( Bioinspired Construction of icronano
Lignocellulose into an Impact Resistance “Wooden Armor” With Bouligand Structure, : Yipeng Chen, Baokang Dang,
Jinzhou Fu, et al, ACS Nano, May 1, 2022, https://doi.org/10.1021/acsnano.1c10725) Copyright © 2022, American
Chemical Society

The artificial wooden armor, with interfacial double layered network, and having “twisted plywood (Bouligand-type)
structures”, is able to withstand lethal blow of impinging high-speed bullets. It has a potential to achieve ∼10 times more
ballistic impact resistance than its counterpart, and is competitive with conventional engineering materials (e.g., ceramics,
glass, and alloys). These specially designed materials are much lighter than typical ballistic impact resistant materials,
including steel, ceramic and glass. Their superior impact-resistant performance and damage tolerance can be attributed to
their unique “Bouligand-like structural design”, which was inspired by the natural Arapaima gigas scale. In general, the
bottom−up strategy of fabricating synthetic wooden armor will inspire and provide a feasible route to design and develop
cost-effective, lightweight, biodegradable, and environmentally sustainable materials which can find potential applications
in the area of military, human security and aviation and so on.
Figure: 4 Comparison of specific ballistic energy absorption of the artificial wooden armor with other common structural
materials. The equation inset is for the specific ballistic energy absorption, where v1 and v2 are the velocities of the bullet
before and after passing through the sample, m is the mass of bullet, and h and ρ are the thickness and density of the
sample, respectively. Reprinted and adapted with permission from ( Bioinspired Construction of Micronano Lignocellulose
into an Impact Resistance “Wooden Armor” With Bouligand Structure, : Yipeng Chen, Baokang Dang, Jinzhou Fu, et al, ACS
Nano, May 1, 2022, https://doi.org/10.1021/acsnano.1c10725) Copyright © 2022, American Chemical Society

The impact resistance of synthetic wooden armor is comparable to that of conventional engineering materials (e.g.,
ceramics, glass, and alloys). It is point to note, the density of the wooden armor is just half that of the above-mentioned
materials. In addition, the formability of the secondary hydrogen bonds in artificial wooden armor reinforces its structural
integrity during impact damage, and this effectively avoids the catastrophic failure unlike that of glass and ceramics where
it is attributable to the presence of primary bonds. These noteworthy features make this lightweight, high-performance,
and sustainable material ideally suitable for impact protection in engineering fields such as aviation, space exploration,
deep-sea exploration, military protection, and other fields that involve extreme conditions.
Author: Yashwant Mahajan, Associate Editor, Nanowerk