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Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics 1 Nanotribology, Nanomechanics and Materials Characterization Studies and Applications to Bio/nanotechnology and Biomimetics Prof. Bharat Bhushan Ohio Eminent Scholar and Howard D. Winbigler Professor and Director NLBB [email protected] Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics © B. Bhushan

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Page 1: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics 1

Nanotribology, Nanomechanics and Materials Characterization Studies and Applications to

Bio/nanotechnology and Biomimetics

Prof. Bharat BhushanOhio Eminent Scholar and Howard D. Winbigler Professor

and Director [email protected]

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

© B. Bhushan

Page 2: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Micro/nanoscale studies

Techniques

Bio/nanotribology Bio/nanomechanics Biomimetics

Materials sci., biomedical eng., physics & physical chem.

NanoindentorMicrotriboapparatusAFM/STM

Materials/DeviceStudies

• Materials/coatings• SAM/PFPE/Ionic liquids• Biomolecular films• CNTs

• Micro/nanofabrication

Collaborations

• MEMS/NEMS• BioMEMS/NEMS• Superhydrophobic surfaces• Reversible adhesion• Beauty care products• Probe-based data storage• Aging Mech. of Li-Ion Batt.

Applications

Numerical modeling and simulation

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Page 3: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics 3

Page 4: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Outline• Introduction

NanotribologyExamples of a magnetic storage device, MEMS/NEMS and BioMEMS/BioNEMS

• Measurement Techniques

• Results and ConclusionsSurface Imaging, Adhesion, Friction and Wear Adhesion, Friction and Wear of CNTsBioadhesion StudiesHierarchical Nanostructures for Superhydrophobicity, Self Cleaning and Low AdhesionConclusions

4

Page 5: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Nanotribology• At most interfaces of technological relevance, contact occurs at

numerous asperities. It is of importance to investigate a singleasperity contact in the fundamental tribological studies.

• Nanotribological studies are neededTo develop fundamental understanding of interfacial phenomena on a small scaleTo study interfacial phenomena in micro- or nanostructures and performance of ultra-thin films, e.g., in magnetic storage and MEMS/NEMS components

Tip - based microscope allows simulation of a single asperity contact

Engineering Interface

Introduction

B. Bhushan, J. Israelachvili and U. Landman, Nature 374, 607 (1995); B. Bhushan, Handbook of Micro/Nanotribology, second ed., CRC Press, 1999;B. Bhushan, Introduction to Tribology, Wiley, NY, 2002; B. Bhushan, Nanotribology and Nanomechanics – An Introduction, Springer, 2005; B. Bhushan, Wear 259, 1507 (2005); B. Bhushan, Springer Handbook of Nanotechnology, second ed., Springer, 2007.

5

Page 6: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Magnetic rigid–disk drive (Bhushan, 1996) MR type picoslider

Diamond like carbon overcoat3.5 nm thick

Al2O3-TiC

Liquid Lubricant 1- 2 nm

Diamondlike carbon overcoat 3-5 nm

Magnetic coating 25 –75 nmAl-Mg/10 μm Ni-P, Glass or

Glass - ceramic 0.78-1.3 mm

Thin–film disk

Example of a Magnetic Storage Device

B. Bhushan. Tribology and Mechanics of Magnetic Storage Devices, 2nd ed., Springer-Verlag, NY, 19966

Page 7: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Microgear unit can be driven at speeds up to 250,000 RPM. Various sliding comp. are shown after wear test for 600k cycles at 1.8% RH (Tanner et al., 2000)

Microengine driven by electrostatically-actuatedcomb drive

Sandia Summit Technologies (www.mems.sandia.gov)

shuttle

springs

gears and pin joint

Stuck comb drive

Examples of MEMS/NEMS and BioMEMS/NEMS

Page 8: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Microfabricated commercial MEMS components

8

B. Bhushan. Springer Handbook of Nanotechnology, second ed., Springer-Verlag, Heidelberg, 2007

Page 9: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

The generating points of friction and wear due to interaction ofa biomolecular layer on a synthetic microdevice with tissue

(Bhushan et al., 2006)

9

Page 10: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

SWNT biosensor

MWNT Sheet

Mechanical properties of nanotube ribbons, such as the elastic modulus and tensile strength, critically rely on the adhesion and friction between nanotubes.

The electrical resistance of the system is sensitive to the adsorption of molecules to the nanotube/electrode.Adhesion should be strong between adsorbents and SWNT.

Force applied at the free end of nanotube cantilever is detected as the imbalance of current flowing through the nanotube bearing supporting the nanotube cantilever.The deflection of nanotubecantilever involves inter-tube friction.

(Chen et al., 2004)

(Zhang et al., 2005)

(Roman et al., 2005)

CNT-based Nanostructures

Nanotube bioforce sensor

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Page 11: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Measurement Techniques

Atomic Force Microscope (AFM) andFriction force Microscope (FFM), 1985

B. Bhushan, J. Israelachvili and U. Landman, Nature 374, 607 (1995); B. Bhushan, Handbook of Micro/Nanotribology, second ed., CRC Press, 1999;B. Bhushan, Introduction to Tribology, Wiley, NY, 2002; B. Bhushan, Nanotribology and Nanomechanics – An Introduction, Springer, 2005;B. Bhushan, Springer Handbook of Nanotechnology, second ed., Springer, 2007.

Surface Force Apparatus (SFA),1968

Scanning Tunneling Microscope (STM), 1981

11

Page 12: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Schematic of a small sample AFM/FFM

Schematic of a large sample AFM/FFM

12

Page 13: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

STM images of a solvent-deposited C60 film on gold coated mica

Results – Surface Imaging and Friction

B. Bhushan et al., J. Phys. D: Appl. Phys. 26, 1319 (1993)CNN Headlines News, 3/18-3/19/93, etc.

13

Page 14: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

μ = 0.006

J. Ruan and B. Bhushan, J. Appl. Phys. 76, 8117 (1994); Y. Song and B. Bhushan, Phys. Rev. B 74, 165401 (2006)National Public Radio, 4/12/95; Business Week, 5/1/95 etc.

Topography and friction force maps for HOPG

14

Page 15: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Friction force map and line plots of friction force profiles for HOPG. Friction force changes discontinuously with sudden jumps. This leads to saw tooth pattern and it occurs due to atomic-scale stick-slip. Can use mechanical model proposed by Tomlinson in 1929.

Direction of motion of sample surface

AFM tip-cantilever

model

Samplesurface

Stick Slip

Periodic interaction potential

Slip event is a dissipative process

Equilibrium position before sliding begins

Atomic lattice constant, a

The tip needs to overcome the energy barrier in order to jump from a stable equilibrium on the surface into a neighboring position. The tip remains stuck until energy stored in the spring is high enough to overcome the energy barrier. 15

Page 16: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Roughness, nano- and macroscale friction data of various samples

Coefficient of Friction

SampleRMS*(nm)

Nanoscale*with Si3N4

tip

Microscalewith Si3N4

ballSi(100) 0.14 0.06 0.47HOPG 0.09 0.006 0.1Natural

Diamond2.3 0.05 0.2

DLC film 0.14 0.03 0.19

*Scan area = 1 μm x 1 μm

Scale effect on friction

J. Ruan and B. Bhushan, ASME J. Tribol. 116, 389 (1994)B. Bhushan et al., ASME J. Tribol. 126, 583 (2004)

16

Page 17: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Comparing the conditions of nanoscale and macroscale tests,there are at least four differences

•Contact size in FFM is small—particles are ejected readily

•Mechanical properties have size effect—properties on nanoscale are superior to the bulk properties

•Applied loads in FFM are low—elastic contact regime (little plowing)

•Small radius of tip results in lower friction

17

Page 18: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Schematic of experimental setupN. Tambe and B. Bhushan, J. Phys. D: Appl. Phys. 38, 764 (2005); Z. Tao and B. Bhushan, Rev. Sci. Instrum. 77, 103705 (2006)

Custom piezo stages for high velocity sliding

Ultrahigh velocity stage (upto 200 mm/s) High velocity stage (upto 10 mm/s)

18

Page 19: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

• Friction mechanisms vary with surfaces• At different velocity regime, different mechanisms dominate friction

N. S. Tambe and B. Bhushan, Nanotechnology 15, 1561 (2004); ibid, 16, 2309 (2005); J. Phys. D: Appl. Phys. 38, 764 (2005);Appl. Phys. Lett. 86, 061906, 2005; J. Vac. Sci. Technol. A 23, 830 (2005); Ultramicroscopy 105, 238 (2005); Z. Tao and B. Bhushan, Rev. Sci Instrum. 77, 103705 (2006); J. Vac. Sci. Technol. A 25 1267(2007)

Friction force on log scaleNormal load = 100 nN

60

40

20

0

Si (100)

Fric

tion

forc

e (n

N)

60

40

20

0

DLC

Meniscus force dominates

Atomic-scale stick slip dominates

Viscous shear dominates

Atomic-scale stick slip dominates

Phase transformation/ tip jump

Velocity (μm/s)100 102 104 106

Friction force on log scaleNormal load = 100 nN

60

40

20

0

Si (100)

Fric

tion

forc

e (n

N)

60

40

20

0

DLC

Meniscus force dominates

Atomic-scale stick slip dominates

Viscous shear dominates

Atomic-scale stick slip dominates

Phase transformation/ tip jump

Velocity (μm/s)100 102 104 106

Velocity (μm/s)100 102 104 106

100 101 102 103

Friction force on log scale (low velocity)

10

5

010

5

0

Fric

tion

forc

e (n

N)

Velocity (μm/s)

Si (100)

DLC

100 101 102 103

Friction force on log scale (low velocity)

10

5

010

5

0

Fric

tion

forc

e (n

N)

Velocity (μm/s)

Si (100)

DLC

Friction force on linear scale

Si (100)

DLC

0 105 2 × 105

Velocity (μm/s)

60

40

20

0

Fric

tion

forc

e (n

N)

60

40

20

0

Friction force on linear scale

Si (100)

DLC

0 105 2 × 105

Velocity (μm/s)0 105 2 × 105

Velocity (μm/s)

60

40

20

0

Fric

tion

forc

e (n

N)

60

40

20

0

Effect of velocity on friction force

19

Page 20: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Contour map showing friction force dependence on normal load and sliding velocity.

N. S. Tambe and B. Bhushan, Appl. Phys. Lett. 86, 193102 (2005); Nature Mat. In Nanozone, Feb. 17 (2005)

Nanofriction maps

20

Page 21: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Nanowear map for DLC illustrating effect of sliding velocity and normal load.

Nanowear map

N. S. Tambe and B. Bhushan Scripta Mat. 52, 751 (2005); Tribol. Lett. 20, 83 (2005).

21

Page 22: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Experimental Schematic MWNT tip and SWNTs suspended on a micro-trench

Average diameter of suspended SWNT bridge is 1.43 nmThe diameter of the MWNT tip is about 100 nm.Method (1) works for flexible MWNT tip while method (2) is suitable for stiff MWNT tip

Adhesion and Friction between Individual Nanotubes

B. Bhushan, X. Ling, A. Jungen, C. Hierold, Phys. Rev. B, 2008

(1) Scan of MWNT tip in lateral direction across suspended SWNT bridge

(2) Ramp of MWNT tip in vertical direction against suspended SWNT bridge

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Page 23: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

(A) Nanotubes came into contact and formed a movable junction.By analyzing the dissipated power of the vibrating cantilever, the kinetic friction between nanotube is proportional to the attenuation of the cantilever amplitude during the initial contact of nanotube:

FF = 4 ± 1 pN(B) The junction slipped to the end of the MWNT tip with the

deformation of the tip.(C) The adhesive force between nanotubes forced the nanotubes to

deform more until they detached from each other.

Multiplying cantilever deflection at the point of detachment with cantilever spring constant gives:

FA = 0.7 ± 0.3 nN

The coefficient of kinetic friction is calculated from FF / FA :µ = 0.006 ± 0.003

Comparable to values reported on graphite on nanoscale.

Scan of MWNT tip in lateral direction across suspended SWNT bridge

Cantilever tapping amplitude

0

16 nm21 nm

Cantilever vertical deflection

-1.2 nm0.8 nm

2.4 µm

A B C

(A) (B) (C)

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics 23

Page 24: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Bioadhesion Studies

• Study surface modification approaches - nanopatterning and chemical linker method to improve adhesion of biomolecules on silicon based surfaces.

B. Bhushan et al., Acta Biomaterialia 1, 327 (2005) ; ibid 2, 39 (2006); Lee et al., J. Vac. Sci. Technol. B 23, 1856 (2005) ; Tokachichu and Bhushan, IEEE Trans. Nanotech. 5, 228 (2006); Eteshola et al., J. Royal Soc. Interf. 5, 123(2008)

24

Page 25: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

STA: StreptavidinAPTES:AminopropyltriethoxysilaneNHS: N-hydroxysuccinimidoBSA: Bovine serum albumin

Sample preparation

25

Page 26: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Schematic representation of deposition of streptavidin (STA) by chemical linker method

26

Page 27: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Adhesion measurements in PBS with functionalized tips

Patterned silica surface exhibits higher adhesion compared to unpatterned silica surface. Biotin coated surface exhibits even higher

adhesion. 27

Page 28: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Biomimetics• Nature has gone through evolution over 3.8 billion years. It has evolved

objects with high performance using commonly found materials.• Biological inspired design or adaptation or derivation from nature is

referred to as biomimetics. It means mimicking biology or nature. Biomimetics is derived from a Greek word “biomimesis.” Other words used include bionics, biomimicry and biognosis.

• Biomimetics involves taking ideas from nature and implementing them in an application.

• Biological materials have hierarchical structure, made of commonly found materials.

• It is estimated that the 100 largest biomimetic products had generated $1.5 billion over 2005-08. The annual sales are expected to continue to increase dramatically.

28

M. Nosonovsky and B. Bhushan (2008), Multiscale Dissipative Mechanisms and Hierarchical Surfaces: Friction, Superhydrophobicity, and Biomimetics, Springer-Verlag, Heidelberg, Germany; B. Bhushan (2007), Springer Handbook of Nanotechnology, second ed., Springer-Verlag, Heidelberg, Germany; B. Bhushan, Phil. Trans. R. Soc. A (in press).

Lessons From Nature (Biomimetics)

Page 29: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics 29

Montage of some examples from nature.

B. Bhushan, Phil. Trans. R. Soc. A (in press).

Montage of some examples from nature

Page 30: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

SEM of Lotus leaf showing bump structure.

One of the crucial property in wet environments is non-wetting or superhydrophobicity and self cleaning. These surfaces are of interest in various applications, e.g., self cleaning windows, windshields, exterior paints for buildings, navigation-ships and utensils, roof tiles, textiles and reduction of drag in fluid flow, e. g. in micro/nanochannels. Also, superhydrophobic surface can be used for energy conservation and energy conversion such as in the development of a microscale capillary engine.

Reduction of wetting is also important in reducing meniscus formation, consequently reducing stiction.

Various natural surfaces, including various leaves, e. g. Lotus, are known to be superhydrophobic, due to high roughness and the presence of a wax coating (Neinhuis and Barthlott, 1997)

NY Times, 1/27/05; ABCNEWS.com, 1/26/05; Z. Burton and B. Bhushan, Ultramicroscopy 106, 709 (2006); B. Bhushan and Y. C. Jung, Nanotechnology 17, 2758 (2006); B. Bhushan and Y. C. Jung, J. Phys.: Condens. Matter 20, 225010 (2008)

Hiearchical Nanostructures for Superhydrophobicity, Self-cleaning and Low Adhesion

Page 31: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Rolling off liquid droplet over superhydrophobic Lotus leaf with self cleaning ability

Page 32: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Wenzel’s equation:

cos cosf oRθ θ=

Roughness optimization model for superhydrophobic and self cleaning surfaces

Droplet of liquid in contact with a smooth and rough surface

Effect of roughness on contact angle

M. Nosonovsky and B. Bhushan, Microsyst. Tech. 11, 535 (2005); Microelectronic Eng. 84, 387 (2007); Ultramicroscopy 107, 969 (2007); J. Phys.: Condens. Matter 20, 225009 (2008); US Patent pending (2005)

Page 33: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

SL 0 LAcos cosfR f fθ θ= −

0 LA 0cos ( cos 1)f fR f Rθ θ= − +

fLA requirement for a hydrophilic surface to be hydrophobic

Cassie-Baxter equation:

Formation of the composite interface

Y. C. Jung and B. Bhushan, Nanotechnology 17, 4970 (2006); B. Bhushan and Y. C. Jung, J. Phys.: Condens. Matter 20, 225010 (2008); M. Nosonovsky and B. Bhushan, Microsyst. Tech. 12, 231 (2006); ibid, 273 (2006)

0LA 0

0

cos for 90

cos 1f

f

Rf

θθ

≥ <+

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Page 34: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

recadv θθ −

)1cosθ(2)cosθ(cosθ1

θθ0

adv0rec0recadv +

−−≈−

f

LAf

RfR

http://lotus-shower.isunet.edu/the_lotus_effect.htm

Increase in fLA and reduction in Rf decrease

Increased droplet volume

Decreased droplet volume

α : Tilt angle

for high contact angle(θ 180°)

θadv : Advancing contact angle

θrec : Receding contact angle

θH = θadv - θrec

B. Bhushan and Y. C. Jung, Ultramicroscopy 107, 1033 (2007); J. Phys.: Condens. Matter 20, 225010 (2008); B. Bhushan, M. Nosonovsky, and Y. C. Jung, J. R. Soc. Interf. 4, 643 (2007); M. Nosonovsky and B. Bhushan, Microelectronic Eng. 84, 382 (2007); Nano Letters 7, 2633 (2007); Springer-Verlag, Heidelberg (2008) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

If θH is low, energy spent during movement of a droplet is small and a droplet can move easily at a small tilt angle

In fluid flow, another property of interest is contact angle hysteresis (θH)

Page 35: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

• MaterialsSample

Poly(methyl methacrylate) (PMMA) (hydrophilic) for nanopatternsand micropatterns

Hydrophobic coating for PMMAPerfluorodecyltriethyoxysilane (PFDTES) (SAM)

Z. Burton and B. Bhushan, Nano Letters 5, 1607 (2005); Y. C. Jung and B. Bhushan, Nanotechnology 17, 4970 (2006); B. Bhushan and Y. C. Jung, J. Phys.: Condens. Matter 20, 225010 (2008);

Low aspect ratio (LAR) – 1:1 height to diameter

High aspect ratio (HAR) – 3:1 height to diameter Lotus patterned

Nanopatterns Micropatterns

Study the effect of nano- and microstructure on superhydrophobicity

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Fabrication and characterization of nanopatterned polymers

Page 36: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Contact angle on micro-/nanopatterned polymers• Different surface structures: film, Lotus, LAR, HAR• Hydrophobic film, PFDTES, on PMMA and PS surface structures

• In hydrophilic surfaces, contact angle decreases with roughness and in hydrophobic surfaces, it increases.

• The measured contact angles of both nanopatterned samples are higher than the calculated values using Wenzel equation. It suggests that nanopatterns benefit from air pocket formation. Furthermore, pining at top of nanopatterns stabilizes the droplet.

LAR HAR Lotus

Rf 2.1 5.6 3.2

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Page 37: Nanotribology, Nanomechanics and Materials ... › kamal3 › nmm › note 4a.pdf · Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Outline • Introduction Nanotribology

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

Transition for Cassie-Baxter to Wenzel regime depends upon the roughness spacing and radius of droplet. It is of interest to understand the role of roughness and radius of the droplet.

Optical profiler surface height maps of patterned Si with PF3

• Different surface structures with flat-top cylindrical pillars:Diameter (5 µm) and height (10 µm) pillars with different pitch values

(7, 7.5, 10, 12.5, 25, 37.5, 45, 60, and 75 µm)

• MaterialsSample – Single-crystal silicon (Si)Hydrophobic coating – 1, 1, -2, 2, -tetrahydroperfluorodecyltrichlorosilane (PF3) (SAM)

B. Bhushan and Y. C. Jung, Ultramicroscopy 107, 1033 (2007); J. Phys.: Condens. Matter 20, 225010 (2008); B. Bhushan, M. Nosonovsky, and Y. C. Jung, J. R. Soc. Interf. 4, 643 (2007); Y. C. Jung, and B. Bhushan, Scripta Mater. 57, 1057 (2007); J. Microsc. 229, 127 (2008); Langmuir 24, 6262 (2008); M. Nosonovsky and B. Bhushan, Ultramicroscopy 107, 969 (2007); Nano Letters 7, 2633 (2007); J. Phys.: Condens. Matter 20, 225009 (2008); Mater. Sci. Eng.:R 58, 162 (2007) ; Langmuir 24, 1525 (2008)

Fabrication and characterization of micropatterned silicon

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Transition from Cassie-Baxter regime to Wenzel regime

Transition criteria for patterned surfaces

• Geometry (P and H) and radius R govern transition. A droplet with a large radius (R) w.r.to pitch (P) would be in Cassie-Baxter regime.

• The curvature of a droplet is governed by Laplace eq. which relates pressure inside the droplet to its curvature. The maximum droop of the droplet

If δ ≥ H

RD)P2(δ

2−≈

Y. C. Jung, and B. Bhushan, Scripta Mater.57, 1057(2007); Y. C. Jung, and B. Bhushan, J.Microsc. 229, 127 (2008); B. Bhushan and Y. C. Jung, J. Phys.: Condens. Matter 20, 225010 (2008)

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Contact angle, hysteresis, and tilt angle on patterned Si surfaces with PF3

Droplet size = 1 mm in radius

• For the selected droplet, the transition occurs from Cassie-Baxter regime to Wenzel regime at higher pitch values for a given pillar height.

B. Bhushan, and Y. C. Jung, Ultramicroscopy 107, 1033 (2007); Y. C. Jung, and B. Bhushan, J. Microsc. 229, 127 (2008); B. Bhushan and Y. C. Jung, J. Phys.: Condens. Matter 20, 225010 (2008) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

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• The critical radius of droplet for the transition increases with the pitch based on both the transition criterion and the experimental data.

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

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Structure of ideal hierarchical surface

• Based on the modeling and observations made on leaf surfaces, hierarchical surface is needed to develop composite interface with high stability.

• Proposed transition criteria can be used to calculate geometrical parameters for a given droplet radius. For example, , for a droplet on the order of 1 mm or larger, a value of H on the order of 30 μm, D on the order of 15 μm and P on the order of 130 μm is optimum.

• Nanoasperities should have a small pitch to handle nanodroplets, less than 1 mm down to few nm radius. The values of h on the order of 10 nm, d on the order of 100 nm can be easily fabricated.

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics

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Fabrication and characterization of hierarchical surface

Fabrication of microstructure

• MicrostructureReplication of Lotus leaf and micropatterned silicon surface using an epoxy resin and then cover with the wax material

B. Bhushan et al., Soft Matter 4, 1799 (2008); Appl. Phys. Lett. 93, 093101 (2008); Ultramicroscopy (in press); Langmuir (in press); Koch et al., Soft Matter (in press)

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Fabrication of nanostructure and hierarchical structure

• NanostructureSelf assembly of the Lotus wax deposited by thermal evaporation

Expose to a solvent in vapor phase for the mobility of wax molecules• Hierarchical structure

Lotus and micropatterned epoxy replicas and covered with the tubules of Lotus wax

Recrystallization of wax tubules

B. Bhushan et al., Soft Matter 4, 1799 (2008); Appl. Phys. Lett. 93, 093101 (2008); Ultramicroscopy (in press); Langmuir (in press); Koch et al., Soft Matter (in press)

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Static contact angle, contact angle hysteresis, tilt angle and adhesive force on various structures

• Nano- and hierarchical structures with tubular wax led to high static contact angle of 167º and 173º and low hysteresis angle on the order of 6º and 1º.

• Compared to a Lotus leaf, hierarchical structure showed higher static contact angle and lower contact angle hysteresis.

B. Bhushan, Y. C. Jung, A. Niemietz, and K. Koch, Langmuir (in press)

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Self-cleaning efficiency of various surfaces

• As the impact pressure of the droplet is zero or low, most of particles on nanostructure were removed by water droplets, resulting from geometrical scale effects.

• As the impact pressure of the droplet is high, all particles which are sitting at the bottom of the cavities between the pillars on hierarchical structure were removed by the water droplets.

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Conclusions

• AFM/FFM has been developed as a versatile tool for fundamental studies in nanotribology, nanomechanics and material characterization.

• It has been successfully used for studies of surface imaging, adhesion, friction, scratching/wear, lubrication, measurement ofmechanical and electrical properties, and in-situ localized deformation studies.

• Examples of nano/biotechnology and biomimetics research are presented.

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Acknowledgements• Financial support has been provided by the Office of Naval

Research, National Science Foundation, the Nanotechnology Initiative of the National Institute of Standards and Technology in conjunction with Nanotribology Research Program, and industrial membership of NLBB.

• The self assembled monolayers (SAMs) were prepared by Dr. W. Eck and Prof. M. Grunze at University of Heidelberg, Germany, and Drs. P. Hoffmann and H. J. Mathieu of EPFL Lausanne, Switzerland.

• Some of the patterned samples were provided by Dr. E. Y. Yoon ofKIST Korea and Drs. P. Hoffmann and L. Barbieri of EPFL, Lausanne, Switzerland.

• The BioMEMS/BioNEMS studies were carried out in collaboration with Prof. S. C. Lee of OSU Medical School.

• Physik Instrumente provided high speed piezo stages.

• Last but not the least, contributions by my past and present students and visiting scientists is gratefully acknowledged.

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References• Bhushan, B., Israelachvili, J. N. and Landman, U. (1995), "Nanotribology: Friction,

Wear and Lubrication at the Atomic Scale,” Nature 374, 607-616.

• B. Bhushan (1999), Handbook of Micro/Nanotribology, second ed., CRC Press, Boca Raton, Florida.

• Bhushan, B. (2001), Modern Tribology Handbook, Vol. 1 & 2, CRC, Boca-Raton, Florida.

• Bhushan, B. (2002), Introduction to Tribology, Wiley, New York.

• Bhushan, B., Fuchs, H., et al. (2004, ’06, ’07, ’08, ‘09), Applied Scanning Probe Methods, Vol. 1-13, Springer-Verlag, Heidelberg, Germany.

• Bhushan, B. (2007), Springer Nanotechnology Handbook, second ed., Springer-Verlag, Heidelberg, Germany.

• Bhushan, B. (2008), Nanotribology and Nanomechanics – An Introduction, second ed., Springer-Verlag, Heidelberg, Germany.

• Bhushan, B. (2008), “Nanotribology, Nanomechanics and NanomaterialsCharacterization” Phil. Trans. R. Soc. A 366, 1351-1381.

• Bhushan, B. (2009), “Biomimetics – Lessons from Nature: An Overview”, Phil. Trans. R. Soc. A (in press).

http://mecheng.osu.edu/nlbb 48

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Questions & Anwers

• Question 1

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Questions & Anwers

• Question 2

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Questions & Anwers

• Question 3

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Questions & Anwers

• Question 4

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Questions & Anwers

• Question 5

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Questions & Anwers

• Question 6

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Questions & Anwers

• Question 7

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Questions & Anwers

• Question 8