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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-03-27
Lecture 7 & 8. Biomimetic Surfaces I
Adhesion & Wetting
Surface Science
As old as civilization
Administering oil to the surface of wooden planks
in ships to reduce friction with water
Deposition of poison on arrowheads

Innovations aimed to endow surfaces with desired


properties through modifying their structures,
compositions, and molecular organizations.
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3
Adhesive
Climb the wall
A "glue" to stick minerals back on eroded teeth
Adhesive in water
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5
Minimize
flow resistance
Swim faster
V.S.
See clearly
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Anti-reflection (AR)
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Superior Anti-reflection Lens
nano-bumps
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Moths Eyes
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SURFACE
Anti-
Scratch
Water
Smudges
Reflection
Dust

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More colorfullife
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Fluid transport
Ultra-Slipperiness Water-Repellency
Fluid Harvesting
Smart Adhesive
Structural Colors
Anti-Fogging
Bio-inspired
SURFACE/INTERFACE
science & engineering
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What you will learn in the next 90 minutes?
Lecture 7. Adhesion
Dry adhesion: gecko feet
Wet adhesion: mussel glue
Lecture 8. Wetting
Liquid repellent: lotus leaf, pitcher plant
Antifogging: moths eye
Water vapor harvesting: namib desert beetle
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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-04-27
Lecture 7. Biomimetic Surfaces I
Adhesion
A Century Debate -
Mechanism of adhesion in the dry adhesive pads
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Mechanism?
Suction cups, capillary, friction,
electrostatic attraction,
microinterlocking, vdW
Discovery?
1970s direct force of single hair
10 times more sticky than
max. adhesion for a whole animal
Force?
Van der Walls
Weakest force between atoms/molecules
When acting collectively, it provides significant
cohesive forces within solids & adhesive forces between solids
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Structure Function
attachment, detachment, self-cleaning
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Structures?
Hierarchical
Fundamental Study:
Johnson et al. developed the JohnsonKendallRoberts
(JKR) model by considering interactions between adhesive elastic
spheres, in which the size of the contact area was determined via
a balance between elastic and surface energies
Micro-hairs: setae
Nano-hairs: spatulae
Experimental: Adhesion Characteristics
1. Anisotropic Adhesion. Geckos toes can actively switch its toe
direction for easy attachment and detachment.
2. Low Normal Detaching Force. The detaching force required for lifting
the geckofoottoe from the contacted surface nearly equals zero.
3. High Compatibility. Gecko exhibits high adhesion capability to wet or
dry and molecularly smooth or very rough surfaces.
4. Self-cleaning and Anticollapse Properties. Geckos setae are made of
elastic protein with a modulus of 24 GPa; -keratin can prevent the
impure contaminations from adsorbing
Hoon, E. J.; Kahp, Y. S. Nano Today 2009, 4, 335.
Structural Requirement for Synthetic Dry Adhesives
1. Small Fibril Radius.
Contact Splitting theory: the adhesion force the fibril radius
2. High Aspect Ratio.
Mechanism of crack propagation in rubbery materials: a high aspect
ratio No. of fibrils to contact the surface, Modulus for
effective elastic energy dissipation
3. Slanted Structures.
Shear and normal contact experiments: an angled structure
significantly lowers the effective modulus of the surface.
A directional angle of the nanostructured fibers is a crucial factor
for anisotropic, reversible dry adhesive (i.e., strong attachment and
easy detachment)
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Fabrication of Synthetic Dry Adhesives
Two main approaches:
1. micro/nanoscale casting (polymers)
using a variety of lithography techniques: e-beam lithography,
photolithography, electrochemical etching, etc
2. gas phase growth (CNTs)
indenting a wax with an AFM tip and then molding polymer
into that wax mold
Metin, S.; Ronalds, F. J. Adhes. Sci. Technol. 2003, 17, 1055..
i) Structures of High Aspect Ratio (HAR)
PDMS: limited the mechanical stability of HAR pillars
2.5 to 25 m in radius and 2.5 to 80 m in height with the aspect
ratio between 0.5 and 4. Critical AR >0.5 AR adhesion
E-beam lithography: HAR but slow and expensive
An array of micropillars made by
micropatterning polyimide hairs.
Scale bars: 2 m.
(b) Upon several detachmentattachment
cycles, its adhesive property degraded
due to hairs breaking and lateral bunching.
Geim, A. K.; Dubonos, S. V.; Grigorieva, I. V.; Novoselov, K.
S.; Zhukov, A. A.; Shapoval, A. A. Nat. Mater. 2003, 2, 461.
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i) Structures of High Aspect Ratio (HAR)
Capillarity-driven Rigiflex Lithography aided by modulated
interfacial tensions
stretched PMMA nanohairs on PET film
Jeong, H. E.; Lee, S. H.; Kim, P.; Suh, K. Y. Nano Lett . 2006, 6, 1508.
ii) Directional Structure
A directional angle of the nanostructure is another crucial factor for
Anisotropic (strong attachment and easy detachment) and reversible
dry adhesions.
Significantly lower the effective modulus of a hair surface and
prevent structural bucking under a preload
a diameter of 8 m and a tilting angle of 25
o
with a good flexibility
and a normal adhesion of 2.53.2 N/cm
2
Good adhesion on glass but difficult demolding without fracturing
Aksak, B.; Murphy, M. P.; Sitti, M. Langmuir 2007, 23, 3322.
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ii) Directional Structure
Thermal annealing
E-beam irradiation
CO
2
gas
A greater adhesion hysteresis:
the strong shear attachment when pulled from the bent direction (31 N/cm2)
contrasted with the easy detachment from the opposite direction (4.1 N/cm2)
Jeong, H. E.; Kim, T.; Kang, T. J.; Yoon, H.; Char, K.; Suh, K. Y.; Tahk, D. Nano Today 2009, 4, 385.
ii) Directional Structure
Shear force: Forward v.s. Reversed
for easy attachment and detachment
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Kim, T.; Jeong, H. E.; Suh, K. Y.; Lee, H. H. Adv. Mater. 2009, 21, 2276..
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ii) Directional Structure
Tilting angle Shear force
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(a) Si master substrates (left) and formed PUA nanohairs (right) with different leaning
angles, Scale bar = 400 nm. (b) Measured macroscopic shear adhesion force with an
adhesive patch having PUA nanohairs with different leaning angles against a smooth
glass surface upon removing preload of 0.3 N/cm.
Jeong, H. E.; Lee, J. K.; Kwak, M. K.; Moon, S. H.; Suh, K. Y. Appl. Phys. Lett . 2010, 96, 043704.
iii) Tips structures
Observed in different animals: spherical, conical, filament-like,
band-like, sucker-like, spatula-like, flat, and toroidal tip
Heavier animals exhibit Finer adhesion
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Beetle Fly Spider Gecko
Terminal elements (circled areas) in animals with hairy design of attachment pads
Arzt, E.; Gorb, S.; Spolenak, R. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 10603.
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iii) Tip structures
various micro-to-nanoscale structures
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del Campo, A.; Greiner, C.; Alvarez, I.; Arzt, E. Adv. Mater. 2007, 19, 1973.
3-D Structure with Special Mushroom-Headed
Mushroom-shaped head was demonstrated to yield the most
significant enhancement of adhesion
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polyurethane fibers cast from a negative silicone rubber mold produced by a
commercial acrylic master mold
Sameoto, D.; Menon, C. Smart Mater. Struct. 2010, 19, 103001.
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3-D Structure with Special Mushroom-Headed
The combination of the tilted fibers and mushroom-shaped tips
can allow for a significant load of 1 kg/cm
2
in shear direction.
Exhibit directional characteristics of gripping when loaded in one
direction, but self-releasing behavior when loaded in the opposite
shear direction.
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34
o
90
o
23
o
23
o
35 m diameter
Michael, P. M.; Burak, A.; Sitti,
M. Small 2009, 5, 170.
iv) Multilevel Complex Hierarchical Structures
Challenge: adhere to surfaces with varying
roughnesses
Each of the fibers deforms independently,
allowing them to access deeper recessions to
make an intimate contact with the surface
Spring-based models predicted: appropriate
multilevel hierarchical structures should
exhibit a higher adhesive force due to
improved adaptation and attachment ability.
two-step photolithography and soft molding
two-step UV-assisted capillary force lithography
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Jeong, H. E.; Lee, J. K.; Kim, H. N.; Moon, S. H.; Suh, K. Y. Proc. Natl. Acad. Sci . 2009, 106, 5639.
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iv) Multilevel Complex Hierarchical Structures
Three-level hierarchical polyurethane fibers:
(a) 400 m curved base fibers; (b) base fiber tip with midlevel 50 m fibers
(c) midlevel fibers in detail; (d) terminal third level fibers at the tip of the midlevel
fibers are 3 m and 20 m in height and have 5 m flat mushroomtips.
Increased adhesion and
interface toughness:
suggesting that a hierarchical
structure could adhere with
higher strength to uneven
surfaces with the roughness
amplitude on the same scale
as the length of the base
fibers
Murphy, M. P.; Kim, S.; Sitti, M. ACS
Appl. Mater. Interfaces 2009, 1, 849.
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Gecko-foot-inspired dry adhesive patch
Jeong, H. E. et al. Adv. Mater. 2011
A dense array of PDMS micropillars
optimal adhesion to skin.
Gecko patch v.s. Conventional patch:
Multiple usage
Smoother peel-off
(slight tilting efficient disengagement)
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Glue on Wet Surface?
Adhesive proteins containing a high content of the catecholic
amino acid 3,4-dihydroxy-L-phenylalanine (DOPA)
DOPA forms extraordinarily strong yet reversible bonds with
surfaces (adhesive force 800 pN/20nN)
Wet Adhesive: mussels
The reduced catechol form of dopa binds surfaces directly for adhesive bonding (left). The
oxidized states of dopa, the semiquinone and quinone, may be reduced by a thiol-rich partner
protein to regain surface-binding ability. Cohesion within the bulk material (right) can be brought
about by metal ion templating and oxidation chemistry, including radical-radical coupling.
J. Wilker, Nature Chemical Biology 2011
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High amounts of DOPA: key to the extraordinary adhesion properties
Fe(III) in the byssus imparts strength and self-healing properties via DOPA:Fe(III)
cross-links. Al(III), Ga(III) and In(III)
Long-last water proof with novel Poly (dopamine
methacrylamideco-methoxyethyl acrylate) (p(DMA-co-MEA)
Synthetic Wet Adhesive
Birkedal, H. et al. PNAS (2011); Biomacromolecue (2013)
Messersmith, P. et al.
Nature (2007); PNAS (2006)
Dual dry/wet adhesives
1. Achieve autonomous switching of adhesion
2. Single-molecule mechanics on different oxide/metal surface
Smart Switchable Adhesive inspired by
mussels and geckos
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Summary
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Lecture 7. Adhesion
Dry adhesion: gecko feet
Mechanism
Structure, Feature, Properties
Synthetic dry adhesive: fabrication
CNTs based; Other functions: self-healing (option for Lit Rev Presentation)
Wet adhesion: mussel glue
Mechanism,
Chemistry
Synthetic wet (/dry) adhesives
Applications (option for Lit Rev Presentation)
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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-03-27
Lecture 8. Biomimetic Surfaces I
Wetting
Pinning
Edge
Liquid
When Liquid sees an Solid Edge: Pinning
Study Pinning: Micro to Nano
Control Pinning: Devices and Materials
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The Need for Highly Repellent Materials
The Sticky Problems
Marine Fouling
Ice Nucleation Drag Creation
Bacterial Fouling
Contamination
Blood Coagulation
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Parker &
Lawrence 2001
Namib
Desert Beetle
Deegan et al. 1997
Coffee Rings
Natures Strategy in Controlling Fluid-Surface Interactions
Bohn and Fedele 2004
Nepenthes Pitcher Plants
Neinhuis & Barthlott 1997
Lotus
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Vapor
Liquid

a
=
a

r
Hysteresis:

Solid

Vapor
Liquid
Contact Angle (CA):
Contact Angle,
Contact Angle Hysteresis,
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Ideal Solid

Vapor Liquid
Contact Angle (CA):
Contact Angle: How Much the Fluid Likes/Hates the Solid

LV
cos =
SV

LS
Young (1805):
Ideal Flat
Wenzel (1936): cos* = rcos
Texture, Wetted
*

max
~ 120
o
(Nishino et al.,
1999)
Surface Chemistry :
Surface Chemistry + Physical Roughness:
Cassie-Baxter (1944): cos* = 1 +
s
(cos + 1)
Texture, Non-wetted
*
D

LV

SV

LS
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MSNBC, a mantis
or *alone does not quantify
Liquid Repellency
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Microscopic Origin:

Solid

a
Contact Line Pinning Resists Liquid Mobility
2. Physical Edge 1. Chemical Edge

a

a
Liquid

Johnson & Dettre (1964)


Microscopic Origin:

Heterogeneous Solid
Liquid

Gibbs (1875)
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Pinning Leads to Contact Angle Hysteresis
Vapor
Liquid

a
=
a

r
Hysteresis:

Gravity
Minimizing (i.e., Removing Pinning)
is the KEY to Design Surfaces with
Extreme Liquid Repellency
Furmidge (1962)

LV
(cos
r
cos
a
) =
mgsin
D
width
Retention Force Gravitational Force
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The Lotus Effect
Barthlott & Neinhuis (1997): The Lotus Effect
Image Credit: Burton, Z. & Bhushan, B. (2005)
Dancing Water Droplet
(Ben Hatton and Lidiya Mishchenko, Harvard)
High Water Mobility
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Mobile
Lotus Effect: Air-cushion
*
Cassie-Baxter (1944)
cos* = 1 +
s
(cos + 1)
Liquid
Air
Superhydrophobic State:
* > 150
o
& * < 10
o
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Year
N
o
.

o
f

C
i
t
a
t
i
o
n
s
Impact of The Lotus Effect
>2500 papers since the inception of the Lotus Effect
Credit: Thomson Reuters ISI Web of Knowledge
T
e
c
h
n
o
l
o
g
i
c
a
l

P
r
o
g
r
e
s
s
Technological Limits
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Technological Limits of the Lotus Technologies
Mobile
Lotus Effect:
Air-cushion
*
Liquid
Air
Wenzel State
Cassie State
Non-Mobile
t Time
Mobile
2. Repellency of Complex Fluids
1. Pressure Stability
Liquid
Air
Liquid
Pressure
Low
LV
Pentane released from a height of 10 cm
3. Self-healing/repairing Physical Textures
Tokay Gecko
Autumn, K., et. al. (2000) Nature 405, 681-685.
Is The Lotus Effect the only way to create
liquid-repellent material (i.e., minimizing )?
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A Liquid Surface: Smooth and Chemical Homogeneous
Textured Solid
Water
Silicon Micro-textures
Canola Oil
Thin-liquid film, (i.e., * ~ 0
o
)
Proof-of-Concept Experiment: The Kitchen Experiment
Thin Liquid
Film
Pitcher Plant Surface
Credits: Bohn & Federle, PNAS (2004)
Adhesive Fluid:
Water-in-Oil
Emulsion
Secretion of
Adhesive Fluid
Lessons Learned from Nature:
Stable Lubricating Film
Immiscibility
Pitcher
plant:
Ant:
Inspiration from Nature: Nepenthes Pitcher Plants
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Chemical Affinity: Like Likes Like
Solid A
Solid B Liquid B
Liquid A
Stable Film
Film
Disrupted
Likes
Likes
Formation of Stable Lubricating Film:
Roughness Amplifies Chemical Affinity
D
i
s
p
e
n
s
i
n
g
S
y
r
i
n
g
e
D
i
s
p
e
n
s
i
n
g
S
y
r
i
n
g
e
Liquid Liquid
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Liquid B Liquid A
Solid with Roughness R
h
H
L
Assumptions: 1) L < L
capillary
; 2) h < h
capillary
; 3) H > h; 4) Immiscibility and Non-reactivity
For Stable Film Formation,
E
1
> 0 & E
2
> 0, where
E
1
= R(
B
cos
B

A
cos
A
)
AB
; E
2
= R(
B
cos
B

A
cos
A
) +
A

B
Design Principle: Modeling the Film Stability
E
A
= R
SA
+
A
E
2
= R
SB
+
B
Dry Partial Wetting
E
1
= R
SB
+
AB
+
A
Complete Wetting
E
2
= E
A
E
2
E
1
= E
A
E
1
Vapor
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Silanized Epoxy
Non-Silanized Epoxy
T = 0s T = 5s T = 10s
Dyed Pentane
Stable Film
Film
Disrupted
1 cm
Lubricating Film
Design Principle: Experimental Verification
E
1
> 0
and
E
2
> 0
E
1
< 0
and
E
2
< 0
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Regular Nano-array
5 m
Random Nanofibers
5 m
Examples of Porous Solids
Functionalized
Porous/Textured Solid
Lubricating Film
Liquid
Tilt
SLIPS: Slippery Liquid-Infused Porous Surfaces
Direct Mimicry of Nature: Insect Repellency
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Technological Performance Comparison
Lotus Leaf-Inspired Technology Pitcher Plant-Inspired Technology
VS
1. Omniphobicity
2. Self-Healing
3. Pressure Stability
4. Repellency to Complex Fluids
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1. Omniphobicity and Ultra-Liquid Repellency
Lotus Leaf Inspired Technology
Pitcher Plant Inspired Technology
Lotus Effect:
Air-cushion
*
Liquid
Air
Low
LV
Liquid
Pitcher Plant Effect:
Liquid-cushion
*
Liquid
Low
LV
Liquid
Liquid
Liquid
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Comparison with Best Synthetic Lotus Surface
1. Omniphobicity and Ultra-Liquid Repellency
SLIPS
Hexane
= 3.0

t = 0.00 s
t = 0.77 s
Hexane
SLIPS
1 mm

Liquid Repellency at Ultra-low Tilt


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2. Self-Healing
Lotus Leaf Inspired Technology
Pitcher Plant Inspired Technology
Lotus Effect:
Air-cushion
*
Liquid
Air
Damage
Liquid
Pitcher Plant Effect:
Liquid-cushion
*
Liquid
Damage
Liquid
Liquid
Liquid
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2. Self-healing and Optical Transparency
5 mm
Damage
Self-healed
T = 0 ms
T = 150 ms
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3. Pressure Stability
Lotus Leaf Inspired Technology
Pitcher Plant Inspired Technology
Lotus Effect:
Air-cushion
*
Liquid
Air
Pressure
Liquid
Pitcher Plant Effect:
Liquid-cushion
*
Liquid
Pressure
Liquid
Liquid
Liquid
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HS Camera
Computer
Syringe
A
d
j
u
s
t
a
b
l
e

S
t
a
n
d
0
Substrate
Liquid
Drop
Tilting Stage,
h
Impact Velocity
Dynamic Pressure
V = (2gh)
1/2
P
d
= V
2
1
2
Terminal Velocity
(Villermaux 2009)
V
T
= ( gd)
1/2

a
3. Pressure Stability Characterization: Drop Impact Test
Drop Impact Test
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21 22 23 24 25 26 27 28
0
1000
2000
3000
4000
5000
6000
7000
8000
Pressure
P
r
e
s
s
u
r
e

(
P
a
)
Surface Tension (mN/m)
0
1
2
3
Sliding Angle
S
l
i
d
i
n
g

A
n
g
l
e
,

)
Deng et al., Science (2012)
Lotus Inspired
Surface
Pressure
Sliding Angle
P
r
e
s
s
u
r
e

(
P
a
)
S
l
i
d
i
n
g

A
n
g
l
e
,

(
o
)
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4. Repellency to Complex Fluids
Lotus Leaf Inspired Technology
Pitcher Plant Inspired Technology
Non-Mobile Mobile
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Lotus Effect:
Air-cushion
*
Time
Pitcher Plant Effect:
Liquid-cushion
*
Time
Mobile Mobile
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Blood P. aeruginosa (bacteria)
4. Repellency to Complex Fluids
Crude Oil
S
L
I
P
S
L
o
t
u
s
-
I
n
s
p
i
r
e
d

S
u
r
f
a
c
e
4a. Persistent Resistance to Biofilm Formation
24 hours 7 days
Under Flow Condition
SLIPS
Lotus-Inspired Surface
Bacteria
Bacteria
Bacteria:
Pseudomonas aeruginosa (Sepsis)
Staphylococcus aureus (Pneumonia, Sepsis)
Escherichia coli (Food Poisoning)
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Self-cleaning
Ice-Repellency Anti-Sticking
SLIPS Whats More
65
Porous/Textured Solid
Lubricating Film
Liquid
Tilt
Oil Repellent Blood Repellent Biofilm-Resistant
Self-Healing Self-Cleaning
Ice Repellent
Pressure Stable
SLIPS
Transparent
Summary
Wong, T.-S. et al., Nature, 477: 443 447 (2011)
Best Inventions using Biomimicry of Year 2011
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SLIPS as the Next Wave of Functional Materials
Anti-Soiling
Anti-Soiling
Anti-Biofouling
Reduced Friction
Anti-Icing
Anti-Graffiti
Defrosting
Reduced Friction
Antiseptic
Anti-Soiling
Anti-Stick
Range of Applications
SLIPS
S
O
L
I
D
L
U
B
R
I
C
A
N
T
Roughness
Porosity
Transparency
Viscosity
Transparency
Boiling Pt.
Freezing Pt.
Biocompatibility
67
Lives in one of the driest deserts: southwest
Africa, but obtains all of the water it needs from
ocean fog due to the unique surface of its back
Microscopic bumps with hydrophilic (water
attracting) tips and hydrophobic (water
repelling) sides cover its hardened forewings,
which it aims at oncoming fog each morning
Namib desert beetle (Stenocara gracilipes)
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Beetle-Inspired Bottle Harvests Drinking Water From Thin Air
More effective than existing fog-catching
nets, and could be used to generate clean
freshwater supplies in arid regions,
refugee camps, and at the tops of
skyscrapers, requiring no pumping.
69
Summary
Lecture 7. Adhesion
Dry adhesion: gecko feet
Wet adhesion: mussel glue
CNTs based; Other functions: self-healing (option for Lit
Rev Presentation)
Lecture 8. Wetting
Liquid repellent: lotus leaf, pitcher plant
Water vapor harvesting: namib desert beetle
Antifogging: moths eyes (option for Lit Rev Presentation)
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Homework of Lecture 7-8
1. Please describe the mechanism of gecko-feet dry adhesion from
the aspect of the structure, feature and functions.
2. Please state the principal of wetting at solid-liquid-air interface.
Due by 04/08/2014
Hand in hard copy of homework at the TA, Xiying Chen, at the
beginning of the 04/08 class
Please contact xchen128@asu.edu for questions.