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Bio Inspired Functional Surfaces For Advanced Applications

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193 views22 pages

Bio Inspired Functional Surfaces For Advanced Applications

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George Sam
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© © All Rights Reserved
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CIRP Annals - Manufacturing Technology 62 (2013) 607–628

Contents lists available at SciVerse ScienceDirect

CIRP Annals - Manufacturing Technology


jou rnal homep age : ht t p: // ees .e lse vi er. com/ci rp/ def a ult . asp

Bio-inspired functional surfaces for advanced applications


Ajay Malshe (2)a,e,*, Kamlakar Rajurkar (1)b, Anoop Samant a,
Hans Nørgaard Hansen (1)c, Salil Bapat d, Wenping Jiang (3)e
a
Department of Mechanical Engineering, University of Arkansas, Fayetteville, AR, USA
b
Department of Mechanical and Materials Engineering, University of Nebraska, Lincoln, NE, USA
c
Department of Mechanical Engineering, Technical University of Denmark, Lyngby, Denmark
d
Department of Microelectronics and Photonics, Nano Institute, University of Arkansas, AR, USA
e
TuffTek Division, NanoMech, Springdale, AR, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Over millions of years, biological subjects have been in continuous combat with extreme environmental
Surface
conditions. The fittest have survived through continuous evolution, an ongoing process. In particular,
Nano manufacturing
biological surfaces, which are the active interfaces between subjects and the environment, are being
Bio-inspired
evolved to a higher state of intelligent functionality. These surfaces became more efficient by using
combinations of available materials, along with unique physical and chemical strategies. Noteworthy
physical strategies include features such as texturing and structure, and chemical strategies such as
sensing and actuation. These strategies collectively enable functional surfaces to deliver extraordinary
adhesion, hydrophobicity, multispectral response, energy scavenging, thermal regulation, antibiofouling,
and other advanced functions. Production industries have been intrigued with such biological surface
strategies in order to learn clever surface architectures and implement those architectures to impart
advanced functionalities into manufactured consumer products. This keynote paper delivers a critical
review of such inspiring biological surfaces and their nonbiological product analogs, where
manufacturing science and engineering have adopted such advanced functional surface architectures.
ß 2013 CIRP.

1. Introduction: drivers for delivering natural surfaces plant surface always attempts to minimize particle adhesion and has
a self-cleaning surface, while a fish skin surface will strive to reduce
Nature, a biosphere, can be considered as a training center for water drag and biofouling. The nano and micro structures of surfaces
engineers and scientists. Nature has developed numerous and and their hierarchical architectures have a substantial impact on
almost-perfect materials, processes, and systems from nano-to- their behavior as environmental interfaces. Therefore, these surfaces
micro-to-macro scales after evolving over millions of years. are ‘intelligently’ engineered using application (environment)-
Natural biological systems are always in continuous combat with specific design architectures, combining morphology (e.g., texture)
the changing environmental conditions, harsh or mild, for survival. and functional chemistries (e.g., hydrophobic wax and peptide
These natural systems have evolved for so long and have sustained nanodots). Various thermo, physical, and chemical principles govern
for the survival of the fittest. Different combating forces (chemical, the surface properties of biosystems, which can be successfully
physical, and functional) acting on natural biological systems mimicked in advanced manufactured products [29,52]. Evans and
(plants, animals, and other organisms) in the environment can be Bryan define the terms structured and engineered surfaces and
considered as actions, and the adaptability of biosystems to these discuss the potential applications of such textured surfaces in the
forces by several unique mechanisms can be considered as the CIRP 1999 keynote paper [63]. Further surfaces at micro and nano
direct reaction necessary for survival. Thus, the word Nature can be scales have been the subject of interest for other applications, for
rightly spelled out as Norms for Adaptability for The Unique Reactive example MEMS and NEMS, microfluidics, magnetic storage media,
Environment. Through evolution, nature has learned to produce the surfaces for optics and chemical engineering etc. These applications
most efficient multifunctional surface structures and has defined of surfaces need high quality metrology techniques to precisely
what could be optimum. Hence, nature can certainly be considered characterize such surfaces [52,199]. Improved adhesion, super-
as the best Production Engineer. hydrophobicity, antireflection and other optical properties, genera-
Biological surfaces are interfaces to the environment and play a tion and preservation of energy, hard and tough surfaces, efficient
critical role in survival [52]. They provide strategic ability to natural heat transfer, antibiofouling, changing color, and self-healing are
systems to adapt to the surrounding environment. For example, a some of the common examples found in biological systems in
nature. These superior functional surface properties have inspired
production industries’ interest [20,167,286] to deliver advanced
* Corresponding author. products. Some of the inspiring biological examples of functional
E-mail address: [email protected] (A. Malshe). surfaces in nature have been introduced in the following section.

0007-8506/$ – see front matter ß 2013 CIRP.


http://dx.doi.org/10.1016/j.cirp.2013.05.008
608 [(Fig._2)TD$IG]
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

2. Examples of natural functional surfaces

2.1. Adhesion

Several insects (e.g., beetles, flies), spiders, and lizards (geckos)


have leg attachment pads, which have the ability to attach to a
wide range of surfaces and are used for locomotion across ceilings
and even smooth vertical walls [12]. The radius of the terminal Fig. 2. (a) Self-cleaning by water droplets on lotus leaf; (b) SEM image of surface
showing randomly distributed micropapillae; and (c) SEM image of single papilla,
attachment in beetles, flies, spiders, and geckos reduces with
exhibiting nanofeatures [193].
increase in size of the creature [11]. This leads to an increased (Reproduced with permission from Elsevier).
number of hairs or setae being packed in an area, which in turn
increases the linear dimension of contact and thus the adhesion
self-cleaning and reduction of drag. The CAH represents the
strength. Geckos have both the highest body mass and the highest
dissipation of energy when a droplet moves along a solid surface.
density of terminal elements.
At a low value of CAH, the rolling of the droplet, in addition to
Typically, a gecko’s foot has 500,000 keratinous hairs or setae
sliding, assists in removal of contaminant particles [20]. However,
(5000 setae/mm2) and is capable of generating 10 N of adhesive
it was observed that condensation of drops on the lotus leaf lead to
force with approximately 100 mm2 of pad area. Each seta is 30–
increased CAH, and thus the mobility of the drops were restricted
130 mm long, only one tenth the diameter of human hair, and has
[41]. On the contrary, Wier and McCarthy demonstrated that
hundreds of projections terminating in 0.2–0.5 mm spatula-shaped
condensation on superhydrophobic surfaces might lead to more
structures (Fig. 1) [12,97]. As the spatulae come in contact with a
water retention than a smooth surface [334]. Therefore, the
substrate, van der Waals interactions produce forces, which are
wetting behavior between a superhydrophobic surface of a lotus
able to support several times the weight of the body due to the
leaf and a water droplet is a complex phenomenon and has been
periodic nature of the setae [104,105]. This is responsible for the
investigated by multiple groups [56,64,65,214,276].
dry adhesion in geckos. When the spatula tip, assumed to be a
Furthermore, the wings of the Morpho aega butterfly also
curved segment of a sphere (radius, R = 2 mm), is separated from a
possess flexible nanotips that are direction-dependent and are
large flat surface by the atomic gap distance (D  0.3 nm), the setal
present on the top of ridging nanostripes and overlapped
force is given by AR/6D2, where A is the material-dependent
microscales (Fig. 3(a) and (b)) [21,257,269,323,326,346,350,359].
Hamaker constant (1019 J) [12]. The van der Waals force per
The quadrate scales overlap each other and have a length of
spatula is approximately 0.4 mN, and the setal force ranges from 40
150 mm and width of 70 mm. Furthermore, there are several
to 400 mN, as there are around 100–1000 spatulae per seta. Due to
ridging stripes (184 nm in width and 586 nm in clearance) on
the large number of spatulae, there is disequilibrium in energy
the surface of each scale. The fine nanostripes are composed of
[(Fig._1)TD$IG]between the wall and spatulae, which leads to self-cleaning. multiple layers of cuticle lamellae of varying dimensions and are
stacked stepwise. The nanotips (slightly tilted and 121 nm in
height, not shown here) are present on top of the stripes. Therefore,
there exists a hierarchical arrangement of micro and nanostruc-
tures made of nanotips on the lamella and stacked nanostripes and
microscales on the wings. This periodic arrangement delivers
superhydrophobic function to the butterfly wing surface. The
water droplet rolls radially outward (RO).
[(Fig._3)TD$IG]
Fig. 1. (A) Mesostructure: ventral view of the foot, with adhesive lamellae visible as
overlapping pads; (B) microstructure: proximal portion of a single lamella with
individual setae in a visible array; (C) and (D) nanostructure: single seta with
branched structure at upper right, terminating in hundreds of spatula tips [97]
(Copyright (2005) National Academy of Sciences, USA).

2.2. Super-hydrophobicity

The surface of a lotus leaf has randomly distributed micro-


papillae that are approximately 5–9 mm in diameter and are
covered by fine branch-like nanostructures (120 nm in dia- Fig. 3. Hierarchical micro and nanostructures on the surface of wings of butterfly
meter). These features are covered by epicuticular waxes (made (a,b): periodic arrangement of overlapping microscales and fine lamella-stacking
nanostripes on the scales in butterfly wings. Inset in (a): M. aega butterfly. Scale
from a mixture of long chain hydrocarbons), which are two- or
bars: (a) 100 mm, (b) 100 nm [359].
three-dimensional structures with a variety of morphologies (Reproduced by permission of the Royal Society of Chemistry).
[68,166]. The 3D structures vary from 0.5 to 100 mm while the
2D wax films vary from a few molecular layers to 0.5 mm
[17,18,168,169]. The multiscale surface features and hydrophobic 2.3. Optical engineering
epicuticular wax on the surface lead to improved water contact
angle and a reduced sliding angle. As a consequence, the surface Colors in nature are produced by pigmentation, iridescence
possesses extraordinary properties such as superhydrophobicity (color change by viewing angle), surface architecture, or a
(static contact angle greater than 1508) and low adhesion. When combination thereof. Natural colors resulting from surface
water droplets fall on the lotus leaf surface, they are almost architectures result from the multilevel interaction of light with
spherical and move freely in all directions [193]. In this process, the highly precise and intricate constructions [141,322]. For example,
water droplets also pick up dirt particles, and this generates a self- in addition to offering superhydrophobicity as discussed above, the
cleaning effect (Fig. 2). This effect is due to the periodicity of the Morpho butterfly also exhibits blue iridescent colors due to the
features at multiple levels (macro/micro/nano) and also due to multiscale arrangement of structures [141,164,247,321,349].
their chemistry. Another common example for amazing natural color is the
A low contact angle hysteresis (CAH) (difference between peacock feather, which exhibits different colors due to complex,
advancing and receding contact angles) is responsible for tiny 2D photonic crystal structure [364]. Variation in lattice
[(Fig._4)TD$IG] A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 609

parallel platelets that change their inclinations simultaneously,


and this in turn changes the distance between them. It was
reported that exposure to light decreases the distance between the
platelets while absence of enough light increases the distance.
Thus, the structural color is dynamic; periodicity of the crystals
changes according to changes in the environment (darkness and
brightness).
Ophiocoma wendtii is a photosensitive species of brittlestars
that demonstrates a change in color from dark brown in the day to
banded gray and black at night [3,101]. This species is also able to
Fig. 4. (a) Iridescent peacock feathers; (b) transverse cross section of the cortex identify shadows and escape from predators. This reaction to light
under high magnification for the green barbule; and (c) longitudinal cross section of is due to diffuse dermal receptors [6,139,221]. The dorsal arm
the green barbules with the surface keratin layer removed [193,364]. plates (DAP) have a single crystal of oriented calcite, which is
(Reproduced with permission from Elsevier).
shaped like a 3D mesh (10–15 mm in diameter) [7,58]. The cross
section shows a regular double lens shape, which is responsible for
constant and periodicity of the photonic crystal structure leads to the photoreception.
the different colors (Fig. 4).
The feather barbs of blue penguins have a biophotonic 2.5. Antibiofouling
nanostructure made up of parallel b-keratin nanofibres arranged
in bundles [191]. The fibers are approximately 184 nm in diameter All marine plants and animals need a reliable mechanism to
and are 3–14 mm long, and the spaces in between the fibers are prevent the growth of fouling organisms on their surface. Shark
filled with air [50]. Short-range order in the arrangement of the skin has placoid scales with a rectangular base implanted in the
fibers at the appropriate size scale, discussed later, is responsible skin with small spines or bristles that emerge from the surface
for generating the blue color by coherent scattering. Phase (Fig. 6). This rough nanotexture on the shark skin minimizes the
separation by spinodal decomposition or nucleation and growth surface area available for the adhering of organisms, which keeps
are projected as the mechanisms for the self-assembly of the the skin clean. Air trapped in pockets formed between scales repels
channel and spheretype barb nanostructures, respectively microorganisms away from the skin. In addition, accelerated water
[61,259]. flow also lowers the contact time of microorganisms. Mucus on the
The dorsal surface of the Japanese jewel beetle shows a color skin also acts as an osmotic barrier against the salty nature of
change from yellowish-green to deep blue when the viewing angle seawater and protects sharks, as well as fish and other aquatic
is changed from the normal to the elytron (forewing) to the tail. On [(Fig._6)TD$IG]
animals, from parasites and infections.
the other hand, the ventral surface changes color from reddish-
brown to green [164]. The elytron is covered with a pattern of
about 10 mm composed of pentagons and hexagons with a hole at
each apex. Transmission electron microscopic analysis of the cross
sections reveals that the patterns are made of epicuticle on the
outer side and exocuticle on the inner side [98,170]. The change in
color is attributed to the multilayer interference due to the
roughness from the different features present on the surface of the
beetle [217,234,241].

Fig. 6. (a) Optical image of fish scales [193] (Reproduced with permission from
2.4. Optical tuning (changing color)
Elsevier). (b) Riblets on shark skin [20] (Reproduced with permission from the Royal
Society of Chemistry).
There are several examples in nature that involve change in
color of a surface according to environmental conditions. The most It was reported that the green feathers of blue-crowned
common example is the chameleon that changes skin color to parakeets have substantial resistance to bacterial degradation
increase its chances of survival [320] (Fig. 5). In addition, the color [85]. Typically, bacterial degradation of feathers releases oligopep-
change also assists to regulate body heat and send messages to tides into the feather medium. Measuring the mean concentration
other chameleons. Underneath the chameleon’s outer skin, there of these by-products revealed that bacterial degradation was faster
are cells, which have a pigment in them called chromatophores. for white and yellow parrot feathers than for black, blue, green, or
The top layers of the chromatophores have red or yellow pigment, red feathers [30,31]. Thus, feather color has a significant effect on
while the lower layers have blue or white pigment. The cell bacterial degradation. The colorful pigments reduce microbial
pigments mix like paint, and this gives different colors to the damage to parrot feathers. Feathers having red psittacofulvins
chameleon skin to suit the surrounding environment. Therefore, degraded less than white or yellow feathers, which contain only
the chemistry of the pigments offers the chameleons their ability short chain psittacofulvins that have fewer double bonds than red
to change color. ones. Psittacofulvins thicken the cortex of the barb, which in turn
Similarly, some species of fish change their skin colors. The cells offers more resistance to bacterial attack. Green feathers are
in the surface of the skin of a tropical fish such as neon tetra are composed of both yellow psittacofulvin and melanin, which also
composed of regular layers of thin guanine crystals that are offer increased resistance to abrasion.
approximately 5 nm thick [164,229]. Each cell has two rows of
[(Fig._5)TD$IG] 2.6. Hard and tough surfaces

Teeth are hard biological tissues that demonstrate excellent


mechanical strength due to their hierarchical structure
[5,200,212,270]. The fundamental challenge that a tooth faces is
to bear sufficient load stresses of food items without being
fractured in the process. The toughness comes from its surface and
subsurface, which provide the ability to dissipate deformation
Fig. 5. Change in color of chameleon skin to match surrounding environment. energy at different layers of its structure. The human tooth, a
(Reproduced under the Creative Commons Attribution 2.0 Generic license). functionally graded structure, has an outer layer (the crown), an
[(Fig._7)TD$IG]
610 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

2.7. Energy scavenging (biomimetic solar cells)

Photosynthesis is an almost faultless cycle of energy manu-


facturing designed by Nature over several hundred millions of
years [153]. In this process, the surface of the plant leaves and
some bacteria use solar energy along with carbon dioxide (CO2)
and water from the atmosphere to generate oxygen and
carbohydrates [23,25,253,264] (Eq. (1)).

6H2 O þ 6CO2 ðsunlightÞ ! C6 H12 O6 þ 6O2 (1)

The CO2 supplied by the atmosphere enters the leaves by diffusion.


Light affects the diffusion process by removing CO2 at the
chloroplast and generating a diffusion gradient. Light also initiates
stomatal openings, which significantly reduce the diffusion
resistance. Therefore, chemical interactions at the molecular level
are used for converting light energy into useful chemical energy
[224]. These reactions provide a great inspiration for solar cells,
which convert solar energy directly into electricity [45], discussed
in the next section on manufacturing.
Another excellent example of a flexible solar material is the fur
and skin of the polar bear, which needs to withstand the arctic cold
temperatures of -50 8C [228]. The bears survive these extreme
temperatures due to a 10 cm thick fat layer covered with fur. The
Fig. 7. (a) Structure of human tooth and enamel [202] (Reproduced with permission
hairs of the fur are transparent and have a hollow structure with
from John Wiley and Sons). (b) Structure of dentin [20] (Reproduced with foam in the core [293]. The air trapped in the hollow, water-
permission from the Royal Society of Chemistry). repelling hairs causes them to be highly insulating in nature.
Furthermore, the skin of the polar bear is black in color, which
assists to capture the sun’s radiation. Light reflects along the length
of the hairs, where only a small portion escapes the dense fur
intermediate layer of dentin, and the pulp chamber in the core part [24,228].
[190,271] (Fig. 7). The outer layer of the crown is composed of a
mineralized tissue called the enamel, while the root part is covered 2.8. Sensing external stimuli
with cementum. The enamel is the hardest, most mineralized
tissue type, and it is this part that has evolved elaborate features to Leaflets of the touch-sensitive Mimosa pudica plant are
resist the propagation of cracks through its structure. The enamel is extremely sensitive to physical touch. They close and the stem
arranged in the form of rods that align together like clusters of dry (petiole) falls rapidly when the leaf surface is touched (Fig. 8). The
spaghetti strands [40] and constitutes about 95 wt% hydroxyapa- folding up of the leaflets occurs in a direction independent of the
tite crystallites, 4 wt% water, and roughly 1 wt% proteins. At direction of the stimulus [8,248]. The swollen part at the base of the
nanometer scales, enamel has been clearly defined as composed of Mimosa leaf is called pulvini, which house the mechano and
periodic nanospheres of amelogenin leading to a structure- photoreceptors that enable the leaves to move dynamically in
function relationship [239]. The rods begin close to the enamel– response to external stimuli [331]. In addition, the leaves also close
dentin junction and extend outwards. Bundles or sheets of rods at night and open again in daylight [311]. This dynamic movement
change direction as they form, causing a phenomenon called is controlled by bioactive chemical substances that differ based on
decussation [202]. The enamel offers continuous resistance to [(Fig._8)TD$IG]the type of plant species [306–310,312–315].
mechanical and chemical attack, including from corrosion (e.g.,
during chewing of food with saliva).
The dentin, which forms the bulk of the human tooth is made of
approximately 70 wt% hydroxyapatite crystals, 20 wt% organic
elements (lipids, proteins, and collagens), and the remainder is
water. The dentin is made up of densely packed tubules (1–3 mm
in diameter with a density of 15,000 tubules/mm2). They start from
the inner part of the nerve space and travel perpendicular from the
point of origin to the tooth surface, ending just below the enamel.
The tubules are made of tiny projections of cells called as Fig. 8. Leaves of Mimosa pudica plant: (a) unfolded leaves and (b) folded leaves after
odontoblasts. This chemical composition and physical structure of receiving stimulus.
the dentin offers elasticity and mechanical strength to the teeth.
Sea urchins eat through stone; however, their teeth survive and Apart from touch sensitive Mimosa leaves, sunflowers also
remain sharp even with repeated use because the tooth self- demonstrate multiple functions of photosensing, actuation (track-
sharpens itself by fracturing at discontinuities [139,159,329]. The ing the sun), and photosynthesis [174].
tooth is made up of the primary plate zone, the keel, and the stone The different examples of bio-inspired surfaces and their
part. The primary plate zone is made up of primary plates, which functions discussed above are summarized in the Table 1. In
are parallel to each other and oblique to the long axis of the tooth addition to the above list of examples, Nature also presents many
shaft. There are calcareous needles in the stone part, which are other functional surface opportunities, such as human skin for
connected to the primary plates by lamellae. The keel is primarily sensing, honeycomb structure for advanced heat transfer, and
made up of prisms. The tooth is also made up of 0.2–0.25 wt% launching and anchoring from Cocklebur seeds. These examples
organic macromolecules, which are primarily proteins [318,333]. are not discussed here due to space limitations.
Similarly, serrated edge architecture in shark teeth allows for The following section elaborates on the design approaches and
aggressive cutting through flesh and bones of prey [219]. These related parameters that Nature has applied to these surfaces to
examples inspire designing of coatings for cutting tools, wear construct unique but simple architectures resulting in environ-
parts, and various other manufacturing operations. ment-specific functions for survival.
[(Fig._9)TD$IG]
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 611

Table 1
Bio-inspired surfaces and their functions.

Examples of bio-inspired surfaces Multifunctions

Feet of geckos, beetles, flies, mussels, tree frogs, Adhesion


arboreal salamanders

Lotus leaf, red rose petal, rice leaf, water striders, Superhydrophobicity
wings of butterfly (Morpho aega) and self-cleaning

Wings of butterfly (Morpho aega), peacock feather, Optical engineering and


blue penguin feathers, Japanese jewel beetle skin superhydrophobicity

Chameleon skin, skin of tropical fish (neon tetra), Changing color


brittlestars (Ophiocoma wendtii), petals of
chameleon hydrangea

Shark skin, feathers of blue-crowned parakeets Antibiofouling and


hydrodynamic

Human teeth, teeth of sea urchins Wear-resistance and


self-sharpening

Photosynthesis by leaf surfaces, polar bear skin Energy scavenging

Mimosa leaf Sensing and actuation

3. Design architecture: integrated approach using physical,


chemical, and functional attributes

Design of a surface is an organization of building blocks with


different physical and chemical constructs to deliver forms and
functions. As discussed in the previous section, Nature has
successfully designed multifunctional surfaces with various
application-specific functionalities. Identifying and understanding
nature’s design parameters can provide an ideal tool box to
fabricate commercial biomimetic surfaces and subsurface engi-
neered products.
Optimization of these interdependent parameters provides
advanced surface functionalities for adaptation. Table 2 lists and
provides a description of various observed parameters.
The following section defines and describes the approach of
each of these parameters in enabling surface functionalities: Fig. 9. (a) Integration and interaction among different parameters; (b) a
representative example of integration of these parameters [300]. (a) and (b)
demonstrate integration and interaction among these parameters and a related
Table 2
example [300], respectively. (a) pictorially depicts interactions and interdependency
List of design parameters of Nature’s Tool Box and their descriptions.
among relevant parameters discussed below. An example of hierarchical organization
Parameter Description of some of these parameters is illustrated through (b) [300].

Texture/topography Collective assembly of features with different


shapes and sizes resulting in unique
morphologies with certain periodicity
arranged features and their periodicity have been observed to
Scale Dimensions of the features and their arrangement
in multiple directions implement tunability of desired functions (e.g., structural color,
hydrophobicity, adhesion, etc.).
Chemistry Surface and subsurface chemistries and material
Example: Topographical arrangement of micro/nanoscale hier-
properties in order to achieve desired
functionality archical surface features made up of epicuticular wax give rise to
superhydrophobic properties of the well-studied lotus leaf [194].
Sensory system Mechanism which senses the changes in the
The wetting of a solid with water in an air environment depends on
environment and provides feedback
the relation between the interfacial tensions between water and
Complementary Subsurface provides a template for the surface air (gwa), between water and solid (gws), and between solid and air
subsurface [52,199] features and also serves as guidance backplane
(gsa) [29]. The different tensions are correlated by the Young’s
Shapes at multiple scales Multiple building blocks hierarchically arranged equation (Eq. (2)).
at different scales to provide surface functionality

Integration of parameters The integration and interaction among the above g sa  g ws ¼ g wa cos u (2)
selected ensemble of parameters to provide
sustainable and evolving structures
Surface texturing of these wax features on lotus leaves enables
formation of stable air pockets, which in turn increases the water/
3.1. Topography (texturing) air interface and reduces the solid/water interface [21,167].
Particle/contaminant adhesion is suppressed due to the minimal
Description: The arrangement of topographical features influ- interfacial area between the textured surface and the particle. As a
ence the way a surface interacts with the environment. This result, contaminants are captured by the water droplet and
arrangement can be isotropic or anisotropic based on the need of removed from the surface. The mechanism for self-cleaning is
directionality in a given application. For example, shark scales and illustrated in Fig. 10. On a smooth surface, contaminants are only
their orientation typically align along the direction of flow of water re-distributed by water droplets. On the contrary, on a textured
across the skin. It involves arrangement or pattern of repetitive surface, neither the contaminants nor the water can adhere to the
shapes with complementary length scales to create a periodic surface, so they attach to each other and the contaminants roll off
topography across multiple length scales. Spacing between the the surface with the water droplet.
[(Fig._10)TD$IG]
612 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

systems), refractive index, band gap (optical effects), and electron


affinity (energy harvesting).
Example: During energy harvesting [153], a series of reactions
governed by the right chemistries of molecules enable the
photosynthesis process. Chlorophyll a is the main pigment that
absorbs solar radiation at 350–700 nm along with other pigments
such as xanthophylls, carotenoids, and chlorophyll b (a modified
form of chlorophyll). The blue-violet and orange-red spectral
ranges are covered by the chlorophyll a pigment while the
intermediate yellow-green-orange part is absorbed by the
accessory pigments.
The structured arrangement of chlorophyll and other reactants
in an array of antennas is called thylakoids. This arrangement is
effective in light capturing. During photosynthesis, absorption of
Fig. 10. (a) On a smooth surface, the particles are redistributed by water and (b) light by chlorophyll leads to a series of electron transfer reactions.
particles adhere to the droplets on a rough surface and are removed from the leaves During a reaction, the oxidation of water into molecular oxygen
when the droplets roll off [17]. forms the photosystem II phase of reactions (Fig. 11). In the
(Reproduced with permission of Springer Science and Business Media).
photosystem I reaction, the electrons migrate through a series of
uphill and downhill steps to generate energy-rich intermediates.
As a consequence, a sequence of light-independent reactions
3.2. Length scale occurs, where the products of light-induced reactions, such as
Adenosine Triphosphate (ATP) and Nicotinamide adenine dinu-
Description: Dimensions of surface features and spacing among cleotide phosphate (NADPH), are used to form C–C covalent bonds
these features are dominant factors in resulting functional of carbohydrates. The different steps in photosynthesis are
behavior of a surface. Also, assemblies of the features along all [(Fig._1)TD$IG]represented in Fig. 11.
three axes determine their packing density, which is shown to be
an important factor, for example when manipulating adhesion and
enhancing resilience to failures during operation. Similarly,
relative aspect ratio of these features has been shown to
significantly change the surface properties, such as features
observed on shark skin. Last but not the least, spatial tuning in
length scales has also been observed to play an important role in
delivering dynamic functionalities, for example optical tuning
observed in a blue damselfish [76].
Example: Antifouling properties of sharkskin rely on the length
scale of features and their aspect ratio. The sharkskin has tiny
individual tooth-like scales called dermal denticles, which are
ribbed with longitudinal grooves aligned parallel to the direction of
water flow, and this causes the water to efficiently flow over the
surface. The V-shaped scales are present over the entire body of the Fig. 11. Key components and processes involved in natural photosynthesis [153].
shark and are 200–500 mm in height with a spacing of 100– (Reproduced with permission from Elsevier).

300 mm. It has been observed that changing the scale, arrange-
ment, and aspect ratios of such surface features have significant 3.4. Sensory system
effect on antifouling properties of a surface [32,318]. Length scale
of these surface features along with their arrangement and aspect Description: Surfaces are interfaces to the environment, and
ratios make such grooved surfaces resistant to the attachment of their dynamic reactive character exists through integrated sensors
fouling species [289]. The longitudinal scales minimize the wall along with their driver systems [52]. Examples are skins of animals
shear stresses and cause the water to flow effectively over the and leaves of plants like M. pudica. Sensors for physical, chemical,
surface due to a 5–10% reduction in drag (as well as resulting optical, and other sensing are typically embedded in surfaces for
friction and wear) [19]. In addition to reducing drag, the improved monitoring environmental changes. The critical backplane, also
flow of water also minimizes the contact time for the fouling called the subsurface, provides a network of communication and
organisms and does not allow them to settle on the surface. The energetics to activate and drive these sensory nodes. Sensory
longitudinal scales also affect the flow in the transverse direction systems, for example, monitor the environment through para-
by restricting the transfer of momentum. Furthermore, the dermal meters such as temperature (skin), wavelength of light (eyes), or
scales realign themselves in response to pressure changes as the pressure changes (Mimosa leaf).
shark moves through water. This creates a continuously moving Example: Leaves of the M. pudica plant respond to an applied
target for the fouling organisms and assists in maintaining a clean external stimulus at the surface. The leaves also close under
surface. various other stimuli, such as touching, warming, blowing, or
shaking. Contractile proteins present in the vacuole membranes
3.3. Chemistry are activated by an ATP-ATPase system, which in turn is ion-
activated by an external stimulus [287]. The movement occurs
Description: Surface chemistry is another important parameter when specific regions of cells lose turgor pressure, which is the
that interacts closely with topography. Material properties at the force that is applied onto the cell wall by water within the cell
surface typically need multifunctionality, and a combination of vacuoles and other cell contents. When the plant is disturbed,
chemistry along with assembly of features deliver adaptability. For specific regions on the stems are stimulated to release chemicals,
example, in teeth, ceramic chemistry at the surface along with 3D including potassium ions, which force water out of the cell
assembly of anisotropic microstructures provides hardness, vacuoles and the water diffuses out of the cells, producing a loss of
corrosion resistance, toughness, and self-sharpening ability cell pressure and cell collapse; this differential turgidity between
[219]. In some other examples, surface chemistry also assists in different regions of cells results in the closing of the leaflets and the
manipulating properties such as contact angle (super-hydrophobic collapse of the leaf petiole [119].
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 613

3.5. Complementary subsurface in contact (Eq. (3)) [149], where E* is the (reduced) Young’s
modulus of the contact pair, and g is the work of adhesion.
Description: Subsurfaces play a critcal role in empowering
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
surfaces to deliver intended functions. Subsurface attributes, such 4 E  a3
F¼  4pE  g a3 (3)
as a sensory system, periodicty of features, and other such 3 R
parameters complement the surface features, providing desired
functions. It can be viewed as a template and/or a ‘backplane’ for
3
the arrangement of features on the surface. In the case where a Fe ¼ g ry (4)
2
subsurface is a replica of the actual surface, it also accounts for the
redundancy necessary for reliability of the overall system, for This analysis can be extended to determine the pull-off force (Fc)
example in the self-sharpening teeth of sea urchins discussed between the spherical contact tip of radius r and the semi-infinite
above (Section 2.6), or rodent teeth [219]. surface as per Eq. (4) [26]. As evident from Eq. (3), the pull-off force
Example: Human skin maintains a body temperature between is directly proportional to the linear contact dimension. This means
37.2 and 37.6 8C, despite fluctuations in the external temperatures. that if one large spherical contact is subdivided into n smaller
This ability is termed as homeostasis (homeo = same, statis = stay- contacts with identical contact areas, the adhesion force rises by
ing), and the skin is an advanced heat exchanger engineered by n0.5. Thus, the force of adhesion increases with the total number of
nature that helps to control homeostasis. The skin has thermo- contacting surface features, which go up with more contact
sensory fibers with receptor endings that are extremely sensitive splitting. So, in the case of gecko feet, hierarchically assembled
to thermal signals [288,291] (Fig. 12). Endings of heat-sensitive features at multiple scales lead to improved adhesion [11].
nerve fibers are located just below the surface of the skin. Each
fiber ending is a distinct sensor [60]. If the blood temperature 3.7. Integration of ensemble of parameters
exceeds the optimum value, then the neurons in the hypothalamus
of the brain (thermostat of the body) sense this and send a signal to Description: Nature demonstrates sustainable integration of
the other nerve centers, which in turn send signals to the blood above mentioned parameters to achieve functional and multi-
vessels of the skin. These feedback signals then cause the functional surfaces. As shown in Fig. 9(a), all the parameters appear
expansion of these blood vessels, causing more blood to flow to have synergistic interplay. These parameters coexist in harmony
close to the body surface, where excess heat is radiated from the and interact symbiotically to yield optimium performance to the
body. On the other hand, a significant drop in temperature causes surface and interface.
contraction of blood vessels, resulting in more blood being retained Example: The effective interplay amongst various parameters
on the skin surface and less heat loss from the surface. In both becomes evident by studying the examples of structural colors
scenarios, an abnormal body temperature is sensed by the observed on peacock feathers and on wings of butterflies. The
specialized neurons, and corrective action is activated to bring brilliant colors are a result of symbiotic interplay between
the temperature back to normal. chemistry, periodically-arranged surface structures in 3D, and
[(Fig._12)TD$IG] resulting photonic bandgap, with length scales on the order of the
wavelength of visible light [164]. Periodical arrangement of cuticle
structure gives rise to a 1D photonic structure observed in case of
Morpho butterflies. As shown in Fig. 13, the wing of male Morpho
didius has a slender cover scale and an overlapping ground scale.
Each scale is made up of several minute ridges with a pitch of 0.7–
1.4 mm and has a lamellar structure of 6–8 alternate layers of
cuticle (0.055 mm thick) and air (0.15 mm thick). The ground scale
has the pigment, which gives a brownish color to the wings. In the
Morpho rhetenor, one of the scales deforms to a small flake while
the other scale has ridges, which are 0.7–0.8 mm apart. The
wavelength of reflected light is a result of a multilayer interference
at cuticle-air interfaces and depends on the periodical spacing and
the refractive index of the cuticle (governed by the chemistry) [29].
A similar approach is observed in peacock feathers yielding to
characteristic colors [292,349]. Further, the addition of sensory
Fig. 12. Sensory fibers ending inside the skin [60].
systems and feedback mechanisms gives rise to optical tuning.
Changing the spacing between the periodic assembly in response
to an external sensory stimulus leads to color tuning [76].
3.6. Shapes at multiple scales and hierarchical assembly
[(Fig._13)TD$IG]
Description: Nature has been observed to use surface structral
building blocks of different shapes and sizes in permutations and
combinations across different length scales. Primarily observed
shapes are nodules, spikes, faceted shapes such as plates, and
others. Hierarchical arrangement of these features is also observed
to play a crucial role across functional boundaries for advanced
functionality. For example, use of micro nodules and nano hairs for
superhydrophobicity of lotus leaves, and use of nanodots and their
spacial arrangements for spectral response of peacock feathers.
Example: Hierarchical assembly of shapes (setae and spactula
tips) at multiple scales is responsible for the dry adhesion in gecko
feet. The term dry adhesion indicates that the adhesion is physical
in nature (van der Waals forces) and can be attributed to the size
and shape of the setae [13,29]. The Johnson–Kendall–Roberts (JKR)
theory for two contacting spheres predicts the force F required to Fig. 13. Scales of different Morpho butterflies: (a) M. didius and (b) M. rhetenor [165].
generate a contact area of radius a when two spheres of radius R are (Reproduced with permission from Dr. Kinoshita).
614 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

Depending on the end goal of the surface in the surrounding Table 3


Producing gecko feet-like features on different materials by various manufacturing
environment, certain parameters have been observed to dominate
processes.
over other secondary parameters. There are significant lessons to
be learned from these biological examples, where systems are Material Process Dimensions Salient features
realized through directed assembly. Poly(glycerol Casting & curing Diameters ranging Adhesion
sebacate from 100 nm to strength of
acrylate) 1 mm, and pillar nanopatterned
4. Bio-inspired surfaces and products, and manufacturing
(PGSA) [207] height varying PGSA was two
from 0.8 to 3 mm times that of flat
To mimick Nature’s advanced functionalities in order to unpatterned
advance products for societal needs, further understanding and polymer.
development of manufacturing science, engineering, and sustain- Fe and Al as Conventional CNTs (200–500 mm A 1 cm2 area
able consumption is needed. The following sections discuss catalysts photolithography long) were deposited could support
manufacturing of bio-inspired surfaces and products and their deposited on on patches that were approximately
applications for extraordinary adhesion, super-hydrophobicity, silicon 50–500 mm wide 4 kg weight
substrate [82]
multispectral optical engineering, thermal and chemical sensing,
antibiofouling, energy scavenging, and wear resistance. Polyurethane Plasma etching 2.8 mm long inclined Significant
acylate (PUA) nanohairs with a increase in
nanohairs on neck diameter of shear adhesion
4.1. Adhesive surfaces poly (ethylene 350 nm and bottom force was
terephthalate) diameter of 700 nm observed
4.1.1. Manufacturing processes and approach (PET) [144] (21 N/cm2)
A prototype of ‘gecko tape’ was produced by mimicking arrays due to reduction
of effective
of flexible plastic pillars with a geometry optimized for collective
modulus to
adhesion. Polyimide hairs were fabricated using electron-beam 26.3 kPa
lithography and dry etching in oxygen plasma [83]. Ten arrays
Vertically Plasma coating Approximately 1011 A strong
were fabricated with an area of 50 mm  50 mm with diameters
aligned single bundles of VA-SWNTs adhesion force
ranging from 0.2 to 0.4 mm, and the height and periodicity varied walled CNTs were packed per cm2 of 29.0 N/cm2
from 0.15 to 2 mm and from 0.4 to 4.5 mm, respectively. The (VA-SWCNT) was reported
perpendicular force required to detach the hairs from a surface was [260,261]
proportional to the density of hairs and was dependent on the (PDMS) on Electron-beam Pillars were 200, 400, The adhesive
height and diameter of the hairs. This implies that the number of Poly(methyl lithography 600 nm in diameter force per pillar
hairs capable of attaching to a surface should increase to improve methacrylate) with 1–3 mm distance was 120  6 nN
(PMMA)/Si between centers and in air and
the adhesion, like observed in gecko feet. The adhesive force also
master [179] 600–700 nm in height 86.3  5 nN in
increased with the increase in the contact area, so larger areas of water. 1 cm2
gecko tape would support heavier objects. A Spider-Man toy surface area of
(15 cm in height and 40 g in weight), used as a demo, was adhesive was able
supported by its hand covered by microfabricated gecko tape. A to transmit 9 N
of force under
contact area of 0.5 cm2 was available and the load carrying
water.
[(Fig._14)TD$IG]
capacity was noted to be 100 g (Fig. 14). [(Fig._15)TD$IG]

Fig. 14. (a) Polyimide hairs fabricated to form the gecko tape and (b) a spider-man toy
clinging to a horizontal glass plate by microfabricated gecko tape on the hand [83].
(Reproduced with permission from Nature Publishing Group).

There are numerous manufacturing techniques that have been


used to develop features mimicking gecko feet design architec-
tures. Typically, microfibrillar surfaces were produced by soft-
lithography using poly(dimethylsiloxane) (PDMS) casts on micro-
fabricated masters with holes of different dimensions Fig. 15. (a) PDMS microfibrils (2.5 mm radius, 20 mm height) formed by soft
[4,26,48,55,84,88,173,252,290]. As PDMS is soft and has low molding on SU-8 photolithographic templates [88]; (b) PMMA nanofibrils (2 mm
surface energy, the structures can be easily peeled off from the long, 80 nm in diameter) generated by hot-embossing and elongation by removal of
mold at high temperatures [145]; (c) fibrils obtained by filling porous AA
masters. Masters are produced by photolithography [51,54] by
membranes [160]; (d) PU fibrils (8 mm diameter and tilting angle of 258) obtained
ablating a metallic surface by lasers [252] and by indenting a wax by soft molding on SU-8 wafers patterned by inclined lithography [4]; (e)
surface by an atomic force microscope (AFM) tip [290]. On the thermomechanical process used to generate angled PP fibers [180]; (f) tilted
other hand, nanofibrils were produced from thermoplastic nanofibers made of PUA produced by local softening using electron beam radiation
materials by hot-embossing [347]. In this process, a polymer melt [163]; (g) double-exposure photolithography used to fabricate SU-8 templates on
which PDMS is soft molded [54]; (h) soft lithography and capillary molding used for
is shaped due to contact with a micro/nanostructured mold by
fabrication of PU structures with complex tip geometry [227]; (i) PMMA fibers
applying heat and pressure. Furthermore, angled fibrillar [4,226] obtained by filling porous anodized aluminum (AA), where microfibers (10 mm
and hierarchical structures [54,96,144,171,227,235] have also wide and 70 mm long) branch into nanofibrils (60 nm wide and 0.5 mm long) [171].
been generated. Table 3 summarizes and Fig. 15 illustrates (Reproduced with permission from John Wiley and Sons).
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 615

performance of various manufacturing processes mimicking 4.2. Super-hydrophobic surfaces


gecko-like features.
4.2.1. Manufacturing processes and approach
4.1.2. Functional surfaces and related product applications Self-cleaning surfaces have attracted the attention of many
Table 4, describes leading and lagging design parameters organizations for the last several years. Mimicking self-cleaning lotus
critical in realizing gecko feet-like adhesive features. leaves, artificial super-hydrophobic surfaces have been produced by
various manufacturing processes such as anodic oxidation [231,249,
Table 4 281,299,304], laser treatment [15,36,157,158,256,335,337], sol–gel
Roles and importance of design parameters for dry adhesion.
processing [67,230,251,284,295], electrospinning [1,2,146,189,203–
Parameters Functions 205,238,358,363], chemical vapor deposition [137,142,176,185,192,
Functionally Topography, length Better adhesion by contact 338], crystal growth [38,66,95,107,223,278,280,298,353], plasma
contributing scale of features, splitting for a particular etching [46,172,237,265], electrodeposition and chemical etching
parameters hierarchical assembly terminal shape, maneuverability [92,182,246,279,285,325,327,355–357], lithography [35,43,59,79,
to variations in surface 102,181,187,215,240,258,282,283,305,324,348,361], and others
Secondary Subsurface, surface Assist primary parameters [(Fig._17)TD$IG](Fig. 17).
parameters chemistry, sensory

A fully functional gecko adhesive has tremendous applications


in biomedical materials and devices, labeling, temporary joints in
the construction industry, and for fixing household items [26]. For
example, the gecko tape can also act as a bonding agent for
surgical applications. In particular, researchers [134] in collabora-
tion with two Boston hospitals developed a stretchable and
biodegradable tape to replace conventional surgical staples and
sutures (Fig. 16). This tape can also be used for delivering drugs by
directly placing on organs, such as the heart. As this tape
eventually breaks down inside the body, there is no irritation. A
biodegradable elastomer is used to fabricate the tape so that it can
be readily combined with drugs. The liquid polymer is poured into
silicon molds having 200–500 nm wide indentations. The molded Fig. 17. (a) cellulose acetate fibrous membrane produced by electrospinning [238]
polymer is then spin coated with biocompatible dextran glue. (Reproduced with permission from IOP publishing); (b) cobalt hydroxide crystalline
nano-pins with diameter of 6.5 nm [107] (Copyright 2005 American Chemical
Upon application of the tape, the capillary forces pull the tissue
Society); (c) submicron pillar structures in p-type Si after buffered oxide etching
into the spaces between the pillars and the glue adheres to the [327] (Copyright 2007 American Chemical Society); and (d) SEM images of
tissue proteins. In another application, a thermally-resistant lithographically patterned surfaces containing 8 mm  8 mm square posts [240]
gecko tape was manufactured with vertically aligned carbon (Copyright 2000 American Chemical Society).
nanotubes (CNTs) [127]. This tape was reported to exhibit high
adhesion strength, easy peel-off, and contamination-resistant
[(Fig._16)TD$IG]behavior. Artificial lotus leaf design architectures were developed on
cotton fibers by depositing CNTs by ultrasonic irradiation [197].
Poly(butylacrylate) (PBA) was used to modify the CNTs for
controlling their assembly and also to improve the affinity of
CNTs for cotton substrates [198]. The surface of a typical fiber is
smooth, consisting of natural veins; each fiber has an average
diameter of around 10 mm. Introducing the CNTs roughens the
surface, and the structure then resembles a lotus leaf. The coating
[(Fig._18)TD$IG] process also changed the color of the white cotton fabric due to the

Fig. 16. (a) Iridescent gecko tape produced from an elastomer covered with
nanoscale pillars and biocompatible glue and (b) the gecko tape broken down in
conditions that mimic the inside of the human body [134].

As the adhesive features of geckos are directional, they stick


only when applied in a particular direction, and the adhesive force
is directly proportional to the tangential force [175]. Hence, these
adhesives also have some applications for part handling in
manufacturing and as aids for human and robot climbing for
reconnaissance missions and space exploration [183]. However,
the behavior of gecko surfaces when subjected to repeated contact
and breakage, effect of temperature and humidity, long-term
reliability in specific environments, and the cost-effectiveness of
fabrication on large areas still need to be understood. Therefore,
Fig. 18. (a) Procedure for coating cotton fibers with CNTs; (b) untreated cotton fiber;
there is further manufacturing research required in this area, and (c) CNT coated cotton fiber; water repellant test on (d) pure cotton fabric; (e) CNT
several questions need to be answered before the gecko-inspired coated cotton fabric; and (f) cotton fabric treated with CNT modified by PBA [197].
adhesives are thoroughly exploited for various applications. (Reproduced with permission from the Royal Society of Chemistry).
616 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

presence of CNTs. This approach can also be extended using other Table 6
Role and importance of design parameters for super-hydrophobic systems.
nanomaterials by substituting the CNTs for nanomaterials with a
similar architecture (Fig. 18). Parameters Functions
In another manufacturing approach, mushroom-shaped elas- Functionally Surface chemistry, Allow formation of stable
tomeric microfiber arrays with a self-cleaning nature were contributing topography, length air pockets to achieve
developed [162]. The self-cleaning tendency was due to the parameters scale of features, super-hydrophobicity and
fibrillar structures with mushroom-shaped tip endings. Thus, tip hierarchical assemby low adhesion for self-cleaning

end shape is an important parameter affecting the performance of Secondary Subsurface, sensory system Assist primary parameters
self-cleaning surfaces. parameters
Aerosol assisted deposition has also been used to produce
superhydrophobic surfaces with high contact angle and low
slipping angle [47]. Furthermore, superhydrophobic and conduc- Multiple functional applications from textiles [126] to glass-
tive multifunctional surfaces have been generated on Ti/Si ware [129] are the drivers for the development of superhydro-
substrate by electrodeposition of polyaniline nanowires [262]. phobic surfaces. Organizations have developed superhydrophobic
The modified surfaces demonstrated superhydrophobic properties poly-lactic acid (PLA) fabrics by UV-photografting of hydrophobic
not only for water, but also for other corrosive environments. silica particles functionalized with vinyl surface group over silica.
Ultrafast laser radiation has been applied to deliver water-repellent This approach can be extended to other materials, and this
silicon-based surfaces with hierarchical micro and nanofeatures provides a robust technique to fabricate water and dust-repellent
[365]. Immersing polished copper surfaces in n-tetradecanoic acid fabrics [14].
ethanol solution has offered a corrosion-resistant coating to the Superhydrophobic surfaces and coatings are also used to
copper surface due to the chemical reaction between copper and n- prevent adsorption of microorganisms on the surface. These
tetradecanoic acid [195]. Table 5 summarizes examples of surfaces demonstrate better antibiofouling performance (dis-
manufacturing methods to deliver superhydrophobic surfaces. cussed above) in comparison to a smooth surface due to the
surface topography and chemical origin of low surface energy
Table 5 material. Also, these coatings have no dangerous side effects
Development of superhydrophobic surfaces on different materials by various
associated with commonly used environmentally-adverse formu-
processes.
lations. A company, Duckworth Outdoor Solutions in Blackpool,
Material Process Salient features Lancashire, has developed an awning fabric swela, Swela Nano
Azide functionalized Chemical Water contact angle as high Clean (SNC), which is permanently water- and dirt-repellent [116].
particulates and surface as 151.68 was attained. The radiant colors of the fabric are maintained for a longer time due
CF3AZO onto alkynyl modification
modified silica
to the self-cleaning property of the fabrics. Similar water-repellent
wafer [250] fabrics have also been developed by Schoeller1 in Switzerland
Polyimide (PI) nanotube Porous alumina Superhydrophobicity of PI
(product name: schoeller1-WB-formula) [130] and by Nano-Tex1
arrays on Si wafers membrane molding nanotube arrays had based in Oakland, CA (product name: Canyon) [125]. In summary,
[362] remarkable resistivity to the textile and fabric industry is one of the most benefited market
acid, weak base, and several
sectors mimicking design architectures from the lotus leaf [345].
organic solvents, also to
temperatures up to 350 8C. Superhydrophobic coatings also have applications in eye-
glasses, architecture, optical windows for electronic devices, and
Concentrated poly(etherimide) Regular replica Developed features
(PEI) solution in 1-methyl-2- molding and demonstrated exciting windows in automobiles [354]. StoCorp [133], a producer of a wide
pyrrolidinone (NMP) [80] temperature-induced thermally responsive range of coating products has developed its patent-protected
phase separation wettability.
StoCoat Lotusan, which is an exterior coating that makes buildings
micromolding
self-cleaning. Automobile manufacturer Toyota is developing side-
ZnO thin film on a corning Pulsed DC Generated hierarchical film view mirrors coated with thin superhydrophobic films that will
glass substrate [339] sputtering demonstrated high water
contact angle (>1608) with prevent wetting and thus provide clean and clear mirrors without
a low contact angle using any wipers [128]. Superhydrophobic coatings have also
hysteresis (28) and low shown the ability to minimize fluid drag for objects in water
reflection over a wide
spectral range.
[242,243,302,330]. The water-repelling nature of the surface
drastically minimizes the solid-water interface interaction and
Nanocrystalline (NC) Ni Electrodeposition Multi-level roughness with
coating on cellulose a low surface energy led to
creates a thin layer of air, which in turn reduces the drag.
acetate film [274] high contact angle (1568), Superhydrophobic coatings successfully developed on gold threads
and also reduced the real have demonstrated this ability to reduce drag. When positions of
area of contact.
gold threads versus time were measured in H2O2 solution, the
Al–Nb alloy films deposited Magnetron Dual-scale porous structure velocity of a superhydrophobic modified gold thread was
on scalloped aluminum sputtering and enhances
approximately 1.7 times that of a normal hydrophobic modified
substrate followed by a anodizing superhydrophobicity
coating of fluoroalkyl gold thread [277] (Fig. 19). Superhydrophobic surfaces are capable
phosphate [77] of offering extra supporting force for objects floating on a water
Silver nanoparticles (Ag NPs) Thermal Contact angle of 1668, low surface and also for those immersed underwater. As super-
on hemispheres of evaporation sliding angle of less than 38. hydrophobic coating increases the vertical component of surface
polystyrene (PS) [340] Wettability could be tension, it can offer 0.4 mN more supporting force per centimeter
adjusted by altering
thickness of silver film and
in comparison to a traditional hydrophobic coating [81,277,279].
size of PS spheres Silicon surfaces have been modified with superhydrophobic
Cubic boron nitride and Electrostatic The biomimetic surface
coatings to use as electrodes of a battery. These coatings help to
titanium nitride (cBN-TiN) spray coating structure is capable of keep the liquid electrolyte away from the electrodes and thus
coatings on a cemented (ESC) followed entrapping application- prevent any reaction from taking place. This in turn increases the
tungsten carbide substrate by chemical vapor specific solid lubricant
[336] deposition (CVD) particles
shelf life of the battery [188].
Superhydrophobic coatings have also been used to make
moisture-sensitive electronic components and devices water-
4.2.2. Functional surfaces and related product applications: proof [121]. Thin fluoropolymer superhydrophobic coatings
Table 6 describes leading and lagging design parameters critical deposited on the surface of field effect transistor devices by violet
in realizing lotus leaf-like superhydrophobic features. photochemical process have eliminated the surface discharge due
[(Fig._19)TD$IG] [(Fig._20)TD$IG]
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 617

Fig. 20. (a) Tightly arranged particles on the rake face of an insert and (b) 3D
[(Fig._21)TD$IG]
structural coating surface mimicking lotus leaf surface morphology.

Fig. 19. (a) StoCoat Lotusan inspired from Lotus leaf [133]; (b) superhydrophobic
gold thread propelled by Pt aggregates; (c) positions of superhydrophobic and
normal hydrophobic modified gold threads [277] (Reproduced with permission
from John Wiley and Sons); (d) Water droplet resting on a modified gas sensor chip
surface [268] (Reproduced with permission from Elsevier).

to the leakage current in conditions of high humidity [268].


Superhydrophobic polytetrafluoroethylene (PTFE) coatings have Fig. 21. (a) SEM image of 3D coating with serrated tips and (b) 3D coating
also been deposited on the surface of microwave antennae to demonstrated superior tool performance to 2D coating and ceramic bulks.
provide an ice-proof layer to prevent the deposition of ice or snow
on these antenna and thus maintain strength of the telecommu- protrusions and troughs that function as load-bearing receptacles
nication signal [344] (Fig. 19). for lubricants [148,209]. These unique features could reduce
As seen from the above discussion, superhydrophobic surfaces adhesion and thus facilitate sliding, and help to improve surface
have tremendous multifunctional benefits for different application finish in machining. Microscopically, the spacing of particles in
sectors.
combination with the infiltrants configures 3D structural archi-
tecture with serrated tips [208], as shown in Fig. 21(a). As it is in
4.3. Surfaces for cutting tools and wear parts
contact with workpiece materials under shear stress, the tips wear
away their soft phase, the binder, while resharpening like rodent
Hardness, toughness, lubrication, and self-sharpening proper- teeth, leading to a consistent surface finish. Tailoring the statistical
ties are critically desired for top-down manufacturing applications distribution spacing (density) of the hard particles and applying
such as turning, milling, drilling, forming, drawing, and other suitable infiltrants could provide well-balanced hardness and
processes. In the scope and given length limitations of this section, toughness. This leads to superior functioning of cBN crystal tips
the authors are presenting novel cutting tool surface engineering during material removal process as compared to its counterparts
for metal turning applications using principles learned from these (e.g., 2D multilayer wear-resistant coatings deposited using
architectures. physical vapor deposition (PVD) and chemical vapor deposition
(CVD) methods, and ceramics) (Fig. 21(b)).
4.3.1. Manufacturing processes and approach
Physical morphology of cutting edges of an insert along with 4.3.2. Functional surfaces and related product applications
coating surfaces on the rake and flank faces are critical for tool Table 7 describes leading and lagging design parameters critical
performance and thus the resultant surface quality of the in realizing lotus leaf, human teeth, serrated shark teeth, sea
machined workpieces. Development of coatings and accordingly urchin, and rodent inspired hard, tough and lubricated coatings.
the right geometry of the cutting edges for machining applications
have been active areas of research and development. The
engineering of surfaces at the nanoscale has become a significant Table 7
Role and importance of design parameters for hard and tough surfaces.
scientific and technology endeavor for a wide spectrum of critical
applications including tribology and machining. In this regard, Parameters Functions
considerable insight can be gained by examining textured surfaces, Functionally Hierarchical assembly, Resist formation of cracks
hard and tough enamel, serrated and self-sharpening surfaces of a contributing chemistry, complementary and mechanical defects,
lotus leaf, human teeth, serrated white shark teeth, sea urchins, parameters subsurface provide redundancy
and rodents. for self sharpening

To achieve serrated shark teeth-like architecture at the cutting Secondary Topography, length Assist primary parameters
edge with self-sharpening functions, patented and patents parameters scale of features,
pending, electrostatic field-assisted directed assembly of pre- sensory system

synthesized cBN nano/micro crystals on the cutting edges is used


in manufacturing [28,208–211]. This arrangement of tightly placed
particles delivers a uniform array and distribution of sharp micro/ One of the important applications of such coating surfaces is for
nano tips on the cutting edge (Fig. 20(b)). Manipulating processing machining, a subtractive manufacturing process by controlled
parameters (electrostatic field strength and physical properties of material removal. The process involves direct contact between
the particles, temperature, and reaction kinetics) related to cutting tool and workpiece materials with specific energy
electrostatic field-assisted assembly and infiltration processes consumption constituents of shearing and friction. Depending
could modify the arrangement of the micro/nano-scale cutting upon workpiece materials, tools, and machining conditions, energy
crystal tips. related to overcoming friction at a tool–chip interface can vary
At the macro scale, the assembly of crystal tips forms a 3D significantly [244]. Based on the molecular dynamic simulation
surface (Fig. 20(c)) similar to a lotus leaf surface featuring study from Romero et al. [267], at a significantly reduced
618 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

dimensional scale, the degree of adhesion at a tool–chip interface is After tumbling with submicron MoS2 particles, the surface
the key contributor to friction. Therefore, any effort in reducing the reservoirs were sealed by the lubricant particles. Tribotests
degree of adhesion would help to alleviate friction. Patent and indicated that this biomimetic design, combined with the use of
patent pending surface coatings engineered at NanoMech for insert lubricant particles can significantly reduce both the coefficient of
rake and flank faces can decrease the friction related to adhesion friction and wear rate during sliding [336].
due to reduced contact areas. These surface coatings, which control
surface morphology similarly to a lotus leaf, can also offer localized 4.4. Optical surfaces
receptacles for sustaining cutting fluids and holding lubricants for
replenishing contact surfaces in machining without cutting fluid 4.4.1. Manufacturing processes and approach
(dry machining) [209]. Such coating surfaces on cutting tools aid to The wing structure of a Morpho Peleides butterfly was replicated
extend tool life and improve workpiece surface finish. by a uniform Al2O3 coating by a low temperature atomic layer
In a similar application, the TuffTek1 division of NanoMech deposition (ALD) process. The alumina replica demonstrated the
applied patented and patent pending cutting tool edges with same optical property (presence of photonic band gap) as the
serrated morphologies, as shown in Fig. 22(a) and (b), respectively original wings. Reflection peaks at the violet-blue range were
[124]. In a comparative study of continuous turning 4340 hardened identified on the original as well as the replicated wings.
steel with hardness up to 53 HRC at MRR of 96.8 mm3/s, such Furthermore, the replicas also had identical functional structures
serrated edges of CNMA432 produced a workpiece with low like the waveguide and beam splitter, which can be used to
surface roughness (Ra) than a highly polished polycrystalline cubic manufacture photonic ICs with high reproducibility at low costs.
boron nitride (PCBN) tipped CNGA432 insert (Fig. 22(C)). Con- On similar lines, the 3D nanocrystalline rutile structure of a Morpho
tinuous exposure of new cBN sharp crystallites from the TiN butterfly was generated from a chitin-based template by a sol–gel
matrix, as the wear progresses, allows continuous shapering of the process [332].
cutting edge allowing improved surface finish over the life of the Inverse opal is a solid material with a 3D architecture, which
coating, unlike traditional PCBN of layered CVD and PVD coatings. is considered as a new generation decorative material in addition
Further, this observation affirms the effectiveness of the serrated to its applications as a photonic crystalline material [89,90,
[(Fig._2)TD$IG] in tearing metallic materials in machining applications.
tips 147,342,352]. Inverse opal films were fabricated on glass
substrates from a suspension of polystyrene spheres (several
hundred microns in diameter) and silica nanoparticles (6 nm
diameter) [91]. The film was first dried in air and then calcined at
450 8C to remove excess polymer and to solidify the nanoparticles.
The films were then exposed to fluoroalkylsilane by thermal
chemical vapor deposition. The inverse opal films developed by
this process on 2 cm wide substrates and the corresponding
microstructure are represented in Fig. 23. Center-to-center
distances between hollow spherical air pockets for the blue,
green, and red films were 275, 310, and 400 nm, respectively.
These air spheres were hexagonally arranged in a silica network
contributing to an optical stop band. A stop band is a 1D photonic
bandgap, which is a spectral range of large reflectivity. Colors can
be observed to a naked eye when the stop band falls in the visible
spectrum.
[(Fig._23)TD$IG]

Fig. 23. (a) Three types of inverse opal films (blue, green, and red) with different
structural periodicity and (b) SEM image of a film with center-to-center distance of
275 nm [91].
Fig. 22. (a) cutting edge with serrated ‘tips’; (b) surface after testing with cBN (Reproduced with permission from John Wiley and Sons).
particles on surface; and (c) comparative chart illustrating improved workpiece
surface finish from edge with serrated tips versus a highly polished edge.
Another application of optical tuning could be for antireflection
surfaces used in applications such as optical imaging, guidance of
optical signals in communication, and others. Several researchers
The other application examples of such coating surfaces would have produced antireflection coatings (with enhanced broad-band
be for wear protection. In reference to a lotus leaf surface transparency) using different manufacturing methods such as fast
morphology coating design, a hard cBN-TiN composite coating was atom beam etching [155], sol–gel process [275,295,341], reactive
used to increase load supporting capacity, and a capping TiN layer ion etching [187,296,301], plasma treatment [138,150,303],
was produced and surface-textured to give biomimetic surface lithography [44,294], colloidal assembly [39,222,343], chemical
morphology. The as-deposited cBN-TiN wear-resistant coating (a vapor deposition [57,297], and layer-by-layer (LbL) [178,184,
hardness of 34 GPa) has a biomimetic surface texture, similar to 186,196].
that of a lotus leaf. In the final part of the design, the surface valleys
constructed among the special surface structures were applied as 4.4.2. Functional surfaces and related product applications
nano/microreservoirs for entrapping application-specific solid Table 8 describes leading and lagging design parameters critical
lubricant particles to reduce friction in tribological applications. in realizing optical engineered surfaces.
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 619

Table 8 applications increases transmission and minimizes glare due to


Role and importance of design parameters for structural coloring.
reflection from optical surfaces [103]. Thus, development of
Parameters Functions structural colors has usage in several critical and consumer areas.
Functionally Chemistry, length Formation of photonic
contributing scale of features, band gap to give rise 4.5. Antibiofouling surfaces
parameters hierarchical assembly, to structural color at
subsurface wide viewing angle 4.5.1. Manufacturing processes and approach
Secondary Topography, sensory Assist primary Different surface topographies were developed on polydi-
parameters system parameters methylsiloxane elastomer (PDMSe) or silicone and the effect of
surface feature size, geometry, and roughness on the settlement of
Ulva zoospores was studied [273]. Earlier studies [32] reported
Several textile fabrics (e.g., Product-Morphotex, [117]), cosmetics, more pore settlement when the topography had 5 mm wide ridges
and paints have been developed based on the structural colors (separated by 5, 10, 20 mm channels) or 5 mm diameter pillars (5,
exhibited by peacocks and butterflies. This phenomena exhibited in 10, 20 mm spacing) (Fig. 25). Narrower channels and pillar spacing
nature can also be used for the displays of cellular phones. These of 2–3 mm were the recommended dimensions to minimize spore
displays would be based on reflected light mimicked from nature. attachment. In light of this, in the study by Schumacher [273], the
These displays would be clearly readable in sunlight and use less different features were included, for example 2 mm wide ribs of
energy, as they will not require an internal source of light [20]. various lengths (4, 8, 12, and 16 mm) termed as Sharklet AFTM [37].
Organizations in South Korea (e.g., Company-Nanobrick, 123) have These and similar patterns were produced on silicon wafers by
used this concept to develop a high-resolution patterning procedure photolithography and developed using reactive ion etching
capable of generating multiple structural colors in a few seconds followed by cleaning using oxygen plasma etching. The topogra-
[161]. The material, named M-Ink, changes color on interaction with a phical features were then transferred to PDMSe by replicating the
magnetic field and is processed using maskless lithography. M-Ink is patterned silicon wafers. The transferred features had a height of
comprised of superparamagnetic colloidal nanocrystal clusters [(Fig._25)TD$IG] mm. The modified PDMSe surfaces were subjected to Ulva spores,
3
(CNCs), a solvation liquid, and a photocurable resin. The CNCs align
themselves to create chain-like periodic structures along the
magnetic field lines. The interparticle distance varies with changes
in the applied magnetic field strength, and this changes the color
produced. After attaining the desired color, it can be locked by
solidifying the photocurable resin through UV exposure (Fig. 24). This
approach for controllable structural color printing has a wide range of
applications in forgery protection and printing technology. Similarly,
companies are developing products that are electrically tunable,
[(Fig._24)TD$IG]called Electrically Tunable Photonic Crystal [123].

Fig. 24. (a) Flexible photonic-crystal thin film with anti-transmission black tape as
the transferred substrate. This tape blocks the transmission of light from the
backside; (b) generation of high-resolution multiple colored patterns using M-Ink;
(c) reproduction of the butterfly Papilio palinurus. The color of the wings in the
reproduced image demonstrates structural color mixing by mixing blue and
yellow-green (scale bar 1 mm). A magnification of the indicated wing area consists
of blue and yellow-green dots. Each dot has dimensions of 16.7 mm  16.7 mm
(1500 dpi) (scale bar 100 mm) [161].
(Reproduced with permission from Nature Publishing Group).

Furthermore, suppressing reflection and enhancing light Fig. 25. PDMSe topographies (a) 5 mm diameter, 5 mm spaced pillars; (b) 5 mm
diameter, 5 mm spaced pits; (c) 5 mm wide, 20 mm spaced channels; (d) 5 mm wide,
transmission are vital in several optical and electro-optical devices. 20 mm spaced ridges; (e) Sharklet AFTM topography. Pillars, pits and channels were
Antireflection surfaces on solar cells makes them more efficient all 5 mm high while ridges were 1.5 mm high [37].
[75,360], while using such coatings in flat panel or detector (Reproduced with permission from Taylor & Francis).
620 A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

Table 9 enhance energy harvesting efficiency. For the reader of this


Role and importance of design parameters for antibiofouling surfaces.
manuscript, in this particular case, mimicking may not be as
Parameters Functions apparent as other applications discussed above.
Functionally Surface chemistry, Resist attachment
contributing topography, length of fouling species, better 4.6.1. Manufacturing processes and approach
parameters scale of features hydrodynamics and fluid Solar cells are typically manufactured using semiconducting
flow in surrounding environment silicon (in single crystal, multicrystal, or amorphous forms) and
Secondary Subsurface, sensory Assist primary parameters have 24% efficiency in converting solar energy to electrical energy.
parameters system, hierarchical Thin film solar cells made of cadmium telluride (CdTe) and copper
assembly indium galium sulfide (CIGS) are also used for electricity
generation at lower costs [10,94,213]. Dye-sensitized solar cells
and their settlement was monitored. The lowest spore density of (DSC) are recently becoming popular for converting solar energy
152  32 spores/mm2 was reported [273]. It was thus found in this to electricity [22,86,87,93,106,151,152,216,218,232,254,255,263,
study that for a given feature width and spacing, the spore density 351].
was dependent on the feature geometry and tortuosity. In another DSCs consist of two transparent conducting oxide (TCO)
study [272] it was found that an increase in aspect ratio also had an electrodes: main working electrode (WE) deposited with a few
effect on the antifouling capability. The spore density of Ulva dropped micron thick layers of TiO2 followed by a coating of organic or
by 42% when there was increase in the aspect ratio. inorganic dye and the counter electrode (CE) with islands of
deposited platinum. There is a spacer between the two electrodes,
4.5.2. Functional surfaces and related product applications and the intermediate space is filled with an organic electrolyte
Table 9 describes leading and lagging design parameters critical containing a redox system such as an iodide/triiodide mixture. An
in realizing antibiofouling surfaces. electron is injected into the conduction band of TiO2 due to photo
As discussed above, the ribbed structure of shark skin scales excitation of the dye. The dye comes back to its original state due to
improves aerodynamic efficiency due to the corrugations having an an electron donation from the electrolyte. An efficiency of 11.5%
effect on the viscous boundary layer of the water. Hence, studies of has been reported for lab-scale DSCs (<1 cm2 active area). The
shark skin have inspired drag-reducing coatings. A transparent following are driver equations:
plastic film having a structure composed of ribs parallel to the
S ! ðh#ÞSþ þ e ðcbÞðTiO2 Þ ðcharge injectionÞ (5)
direction of flow minimizes aircraft drag by 8%, which in turn
reduces fuel consumption by approximately 1.5%. This textured
Sþ þ l
3 ! S þ l2 þ l ðdye regenerationÞ (6)
surface also helps to keep the surface of the aircraft clean [16].
Companies like 3 M have been largely interested in such applications
Sþ þ e ðcbÞ ! S ðrecombinationÞ (7)
[3MTM ScotchcalTM Drag Reduction Film, 132]. Every year, the Navy
spends approximately $550 million to $600 million on powering
I þ e ðcathodeÞ ! 3I ðregeneration of mediatorÞ (8)
its ships and submarines. Out of this expense, at least $50 million is
from the drag due to marine growth fouling the vessels’ hulls. where h = Planck’s constant = 6.626  1034 J s, n is frequency of
Therefore, the Navy is constantly funding work to obtain a nontoxic light, and cb stands for conduction band. These reactions are similar
coating to reduce the routine cleaning of fouled ships. to the series of redox reactions during photosynthesis in nature.
Sharklet Technologies has come up with SharkletTM SafeTouch, In another solar cell design and manufacturing approach,
which is a new line of defense against bacteria. It consists of organic or inorganic hole transporters have been used to transfer
durable skin patterned with several microscopic Sharklet dia- charges between the cathode and the dye instead of conventional
monds that have been proven to prevent the growth of bacteria by electrolytes. The hole transporter is spin-coated after dye
80%. The skins are applied to high-touch bacteria-prone areas such deposition on oxide layers. Recent manufacturing research is also
as restroom stall doors, door push panels, and door push bars [131]. focused on using ionic liquids, gels, and polymers as electrolytes.
Antimicrobial fabrics inspired by the shark skin have been used Several metalloporphyrins and their derivatives have also been
in swimsuits. These swimsuits are manufactured from sophisti- explored as photosensitizers for DSC as they have better broad-
cated fibers and weaving methods replicating the topography of band absorption [9,33,34,42,62,78,99,100,140,143,156,177,201,
scales on shark skin. The suits cling tightly to the swimmer’s body 206,225,233,236,245,266,328] (Fig. 27). One of such derivatives,
and are capable of offering the swimmer a six meter equivalent carboxyphenyl-substituted porphyrin (ZnTPPC), has also demon-
head start due to the dampening of turbulence in the layer of water strated the ability to inject charges into the conduction band of
[(Fig._26)TD$IG]
next to the skin [111] (Fig. 26). TiO2 [49,154,319].

4.6.2. Functional surfaces and related product applications


Table 10 describes leading and lagging design parameters
critical in realizing energy scavenging surfaces.
A Japanese company, Aisin Seiki, has developed a monolithic Z-
type interconnected module based on DSC technology that uses
carbon as interconnect and counter electrode material [232]. These
modules showed 20–30% more energy harvesting efficiency under
real test conditions in comparison to polycrystalline silicon. The DSC
efficiency does not depend on temperatures between 25 and 65 8C,
Fig. 26. (a) Trials on an aircraft coated with a plastic film with same microscopic and the light capturing is less sensitive to the incident angle of
structure [16] (Reproduced with permission from Nature); (b) SharkletTM
SafeTouch inspired from shark skin [131]; (c) Shark skin-inspired high efficiency
radiation. Thus, the DSC modules have been widely used, as they are
swimsuits with antibacterial effect. Arrows show antimicrobial features mimicking economical, stable, easily available, and environmentally friendly.
shark skin microtopography [289] (Reproduced with permission from Elsevier). DSC panels have been used in the walls of the Toyota Dream House
providing solar energy to the building occupants [135,232].
4.6. Energy scavenging surfaces In addition to solar energy, nature has also inspired innovations
in the wind turbine industry. The main factor affecting the
Industries have mimicked fundamental approaches of Nature performance of wind turbine blades is the angle, which the blade
for using surface and subsurface chemical and electro-chemical makes with the incident wind (angle of attack) [74]. Unfortunately,
reactions as well as physical structures to harvest energy and/or increasing this angle causes the blade to stall. To resolve this issue,
[(Fig._27)TD$IG] [(Fig._28)TD$IG]
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 621

Fig. 28. (a) Humpback whale flipper with tubercles; (b) windmill blade with tubercles
designed by WhalePower Corp.; and (c) performance of blade from WhalePower Corp.
(circles) in comparison to standard wind turbine blade (squares) [74].
(Reproduced with permission from Oxford University Press).

4.7.1. Manufacturing processes and approach


Fig. 27. (a) Synthetic routes for the construction of various shaped porphyrin arrays Inspired by the touch sensitivity of M. pudica and other similar
[9] (Copyright 2009 American Chemical Society); (b) zinc phthalocyanine examples, researchers have manufactured haptic (from the Greek
sensitizers on TiO2 surface [140] (Copyright 2009 American Chemical Society);
word haptesthai, which means to touch) fabrics by knitting smart
(c) arrangement of P10 and P18 dyes on TiO2 surface [225] (Copyright 2009
American Chemical Society); (d) Zn(II)-tetra(carboxyphenyl)porphyrins in solution materials with touch therapy features. Manufactured fabrics are
and bound to metal oxide (TiO2, ZnO, and ZrO2) nanoparticle films [266] (Copyright furnished with actuators and sensors that perform duties such as
2007 American Chemical Society). artificial massaging and aromatizing functions while a person
walks [317] (Fig. 29). This fabric is a matrix of clothing embedded
with elements that enable transfer of information by means of heat
Table 10
sensors, liquid diffusion, and mechanically-driven textural sensa-
Roles and importance of design parameters for energy scavenging.
tion. The user can control the system through a feedback
Parameters Functions [(Fig._29)TD$IG]embedded microphone in the clothing.
Functionally Surface chemistry, Improve light collection, charge
contributing topography, transport, and separation for
parameters complementary better efficiency
subsurface

Secondary Length scale, Assist primary parameters


parameters sensory system,
hierarchical assembly

Fish et al. in the Biology department at the West Chester University


of Pennsylvania studied the flippers of humpback whales (Fig. 28)
[69,70,72–74,110]. These whales have a pattern of bumps called
tubercles on their flippers, which enable them to make tight turns
while catching their food. The whales were found to use their
flippers at higher operating angles before stalling. Due to the
tubercles, the flippers had an enhanced lift and a reduced drag
[71,220,316]. Furthermore, the airflow was modified more in the
direction of the flipper and not perpendicular to the flipper.
WhalePower Corp. [136] manufactured tubercle wind turbine
blades using traditional top-down manufacturing. It was reported Fig. 29. (a) Touch-sensitive fabric model [289] (Reproduced with permission from
that due to the tubercles, the operating angle increased from 118 to Elsevier) and (b) Tap Tap scarf designed to simulate human touch. [27].
178 and the performance increased by 40%. An open field test
performed by the Wind Energy Institute of Canada (WEICan) Similarly, a project was developed at the MIT Media Lab to
showed that the WhalePower Corp. turbine blade definitely construct a system of wearable sensors and actuators that can
out-performed the standard turbine blades [74]. In additional collect and play back different types of nurturing human contact
applications, this design has also been used in fans, pumps and for emotional therapy [27]. The researchers developed Tap Tap, a
compressors. scarf that can be wrapped around the body to feel the simulated
touch. Different actuators mounted on flexible plastic sheets are
4.7. Actuating and sensing surfaces to external stimulus placed in different pockets of the scarf and these actuators are
connected to the conductive snaps, which provide power for
Industries have mimicked the fundamental approach of Nature driving the solenoids and heat pumps. The sensory system can be
for using surface and subsurface sensors as well as a smart sensory removed from the scarf and reused. A sophisticated version of the
network of M. pudica and human skin to deliver reactive functions scarf would have coin motors as actuators. This work is novel as it
such as feel and touch. is the first step in making human contact available in ways as never
622 [(Fig._31)TD$IG]
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628

before seen. Such a scarf would be a comfortable and personalized


garment that a parent could leave with their child or a therapist
with their patient to offer an element of nurture and affection.

4.7.2. Functional surfaces and related product applications


Table 11 describes leading and lagging design parameters
critical in realizing actuating and sensing surfaces.

Table 11
Roles and functions of design parameters for actuating surfaces to external stimuli
and for surface sensing.

Parameters Functions

Functionally Sensory system, Sense external stimulus


contributing complementary and actuate the response
parameters subsurface by networking signals

Secondary Topography, Assist primary parameters Fig. 31. (a) Closed molecular network below activation threshold in shape memory
parameters chemistry, length alloy and open molecular network above activation threshold [53] (Reproduced
scale, sensory system, with permission from Elsevier); (b) ‘‘Oricalco’’ shirt with Nitinol fabric [120]; (c)
hierarchical assembly artificial skin developed from nanomaterials [112]; and (d) SmartSkinTM
manufactured by Midè Technology Corporation [122].

Sensitivity to external stimuli has a wide range of applications. conduction, and they have desired thermal and mechanical
Children with autism spectrum disorders feel calm with pressure. properties identical to that of human skin (Fig. 31(c)). Also, the
For such children, a vest ‘hug from a distance’ has been designed nanotubes are biocompatible and are not rejected by the body as a
which can be electronically controlled to give someone a hug over foreign object.
the Internet. The vest imitates the strength, length, temperature, In another product design approach, shape memory alloys
and heart rate of the actual hug. By means of Bluetooth technology (SMAs) are applied for achieving embedded actuation. SMAs
and a cell phone, a hug can be sent to someone wearing a Hug undergo phase transitions due to temperature variations, which
Shirt1 [Company: CUTECIRCUIT, 115] or Hug Jacket to simulate the in turn modify the structure. Based on this property, a secondary unit
feeling of the hug [114]. of Mitsubishi Heavy Industries Ltd. manufactured a shape memory
There are haptic sports garments that use tactile signals to help polyurethane polymer called Diaplex used in nonporous mem-
sportsmen optimize their performance. Such garments have being branes [53]. Micropores are formed due to the micro-Brownian
tested on rowers. Sensors in the garments measure the speed of the motion of material molecules when the temperature goes beyond
rower and how it coordinates with leg and body movements. As the phase transition temperature. This in turn generates a
the rower deviates from the optimum speed or rhythm, pads at the temperature-dependent permeability. This material has been
ankle and waist start vibrating at the correct stroke interval in exploited by several companies such as REI, Timberland, New
order to help the rower to recapture the correct rhythm. Haptic Balance, etc. [53] to manufacture breathable and waterproof fabric
suits also assist in teaching physical activities to people requiring with temperature-dependent insulation/permeation properties
sports training, motor rehabilitation after neurological damage, based on environmental and bodily conditions. The molecular
dance, postural training for health, etc. [Product-Move, Company- sensing network of the shape memory polyurethane polymer below
Electricfoxy; 118]. The sensors analyze body movements and and above the activation threshold is represented in Fig. 31(a).
provide instant tactile feedback to the user [114]. Nitinol SMA wires have been woven into fabric substrates,
Haptic gloves are shaped like human hands and receive which enable them to offer a thermal response. The thermally-
stimulation along the fingertips that mimic the actual physical induced shortening property of Nitinol has been utilized in these
contact with an object or another person. These gloves offer fabrics. Such clothing can adapt itself to the surrounding
unlimited movement to the user in virtual space [114]. An environment and protects the user from the variable weather
extension of these haptic gloves is the musical hepatic gloves, conditions. Furthermore, shirts whose sleeves roll up when it
which help the users to create musical compositions by linking becomes too hot are also manufactured. For this purpose, alloys
hands together. Each participant wears the gloves, headphones (to with a martensite phase temperature between 38 and 45 8C have
hear own music), and clip-on box housing circuits. When the been used. This effect is also seen in the Oricalco shirt
participant touches the gloved hand of another member, they can manufactured by Grado Zero EspaceTM (Fig. 31(b)) [120]. A fabric
hear their music blended with the other person’s sound [108] wetsuit for divers, SmartSkinTM, has been developed by Midè
(Fig. 30). These products have a significant impact on the digital Technology Corporation (Fig. 31(d)) [122]. The passive outer layer
[(Fig._30)TD$IG]cyber informatics revolution. is made up of closed-cell Neoprene foam while the active inner
layer is made up of a hydrogel polymer consisting of a copolymer of
hydrophilic and hydrophobic components. The material undergoes
volume variations around a transition temperature, which can be
adjusted depending on the concentration of the components. The
material swells when below this temperature, and it shrinks when
above. If the diver’s temperature surpasses the threshold, the
material shrinkage increases the water intake which in turn keeps
the skin of the diver cool. On the other hand, a drop in temperature
swells the gel and reduces the water flush.

Fig. 30. (a) Haptic sports garments [109]; (b) haptic suit for improved learning [114]; 5. Summary and future directions
(c) haptic gloves in virtual environment [114]; and (d) musical haptic gloves [113].
Surfaces of natural living subjects serve as the interface
For selective nanomanufactured sensory applications, research between subjects and their diverse environments. Millions of
scientists have employed carbon nanotube technology to replicate years of continuous combat between living subjects and adverse
skin characteristics [112]. Carbon nanotubes were selected as they environment conditions have forced continuous surface evolution,
are temperature and pressure sensors, flexible for electrical resulting in robust surfaces with unique functional properties that
A. Malshe et al. / CIRP Annals - Manufacturing Technology 62 (2013) 607–628 623

Table 12 repetability of manufacturing and performance of bio-inspired


Summary of bio-inspired surfaces for advanced manufacturing.
surfaces, and comparison of those with their natural counter parts
Functions from nature Manufacturing Parameters Product will be an important area of scientific and engineering endeavor.
processes applications
Also, developing understanding of bio-inspired functional surface
Adhesion: feet Soft-lithography, Physical texture: Gecko tape, architectures on productivity of sub-systems and systems, qualita-
of geckos, beetles, hot-embossing, diameter and adhesives in wood
flies, mussels, plasma etching, height of pillars, products, part tive as well as quantative, along with producibility and predictability
tree frogs, arboreal electron beam periodicity of handling in will be vital for maturation of this field.
salamanders lithography, soft features manufacturing,
molding followed aids for human and
by inclined robot climbing for Acknowledgements
lithography, reconnaissance
electron beam missions and space
radiation explorations The authors thank Chairman, Vice-Chairman, Secretary and
other colleagues of STC-S for their continuous feedback during the
Super hydrophobicity: Anodic oxidation, Chemical Water- and dust-
lotus leaf, red rose laser treatment, composition and repellent fabrics, course of the development of this manuscript. The authors extend
petal, rice leaf, sol–gel processing, hierarchical eyeglasses, special appreciation to Prof. De Chiffre, Prof Evans, Prof.
water striders, electospinning, surface geometry architecture,
wings of butterfly lithography, optical windows
Karpuschewski, and Prof. Lucca for critical comments. Two authors
(Morpho aega) chemical vapor for electronic (APM and SB) thank funding support from the National Science
deposition, crystal devices, and
Foundation (NSF) VICTER grant. Also one of the authors (APM)
growth, plasma windows in
etching, automobiles, thanks NSF (Award #: 0927541 and 1000912) for partial support.
electrodeposition, exteriors coating One of the authors (KR) thanks National Science Foundation (NSF)
chemical etching, for self-cleaning
ultrasonic buildings,
for funding support (Grant#: CMMI-1137981).
irradiation, electrodes in
sputtering battery,
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