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You are on page 1of 101

**Diﬀusion at the Nano-Scale
**

by

Pong-Yu (Peter) Huang

MFL TR 2006-01

Microﬂuidics Laboratory

Division of Engineering

Brown University

Providence, RI 02912

October 2006

This report is the PhD thesis of Peter Huang, supervised by Prof. Kenneth Breuer in the Division

of Engineering, and submitted to the Graduate School at Brown University in September 2006.

For more information contact: kbreuer@brown.edu

i

Abstract

Aqueous boundary solution slip at a solid surface and hindered diﬀusion of suspended near-

surface particles are experimentally investigated with a three-dimensional total internal reﬂection

velocimetry (3D-TIRV) technique. The sub-micrometer penetration depth of evanescent wave oﬀers

low-background-noise images where a 10-nm displacement can be accurately measured. At shear

rates less than 1800 sec

−1

, a shear-induced slip length of less than 100 nanometers is observed

at a glass surface of sub-nanometer roughness. Surface hydrophobicity is also found to aid slip.

However, the notion that electrokinetic and electrostatic forces acting on charged tracer particles

lead to slip length measurement inaccuracy is disputed by experiments conducted with aqueous

solutions consisting of electrolytes, which report slip length of similar magnitudes. Anisotropic

hindered diﬀusion of suspended near-surface particles is demonstrated with simultaneous three-

dimensional measurements. Hindered diﬀusion coeﬃcients of 1.5-µm radius particles within 300

nm from the solid wall are shown to be in close agreement with previously published theories.

Lastly, eﬀects of hindered diﬀusion and wall presence on the accuracies of TIRV and other near-

surface measurement methods are studied via Brownian dynamics simulations. The results reveal

that hindered diﬀusion causes a minor bias toward values obtained at the wall if a small interval is

allowed between successive image acquisitions, while particle drop-outs lead to over-estimation of

ﬂuidic velocity values if the time interval between image acquisitions is large. It is also found that

the apparent velocities of near-wall particles are not time-invariant. Still, true ﬂuidic velocity values

can be obtained from the particle apparent velocities with proper scaling. Such scaling correction is

applicable to particle tracking velocimetry measurements, but not to correlation based velocimetry

measurements for their lack of accounting of particle drop-outs. Shear eﬀect on near-wall particle

translation in a ﬁnite imaging depth results in an asymmetric apparent velocity distribution, which

is another potential source of error for correlation based velocimetries. These ﬁndings lead to a

conclusion that particle tracking based velocimetry methods, such as TIRV, are more superior than

correlation based velocimetry methods are in making near-surface ﬂuidic measurements.

Copyright, c _, Pong-Yu (Peter) Huang, 2006

i

Pong-Yu (Peter) Huang was born in Taipei, Taiwan and attended schools there until the

age of ﬁfteen. After graduating high school from International School Manila in 1996,

he attended Cornell University where he received a Bachelor of Arts degree in physics in

2000. Upon graduation, he enrolled at the Division of Engineering, Brown University,

to pursue a graduate degree under the guidance of Professor Kenneth Breuer. In 2002,

he completed a Master of Science degree in engineering, and continued to pursue a

Doctor of Philosophy degree since 2003. He currently resides in the New England region

with his wife and plans to pursue an academic career. Mr. Huang enjoys travelling and

anything related to baseball (except sabermetrics), and holds great interests in economic

perspectives of events in the world. He is a proud fan of the New York Mets since 1999.

ii

This dissertation consists of experimental studies of boundary slip and hindered diﬀusion in

the nano-scale. Included are an overall review and summary of the whole dissertation in the

ﬁrst chapter, and a collection of journal papers, each as a subsequent chapter, with details of

experimental methods and results. The contents of the chapters are:

Chapter 1. Introduction. Including basic concepts of slip ﬂow, hindered diﬀusion and total

internal reﬂection velocimetry, reviews of previously published works, and discussions of the main

results obtained.

Chapter 2. Paper 1. “Near-surface velocimetry using evanescent wave illumination” by Song-

wan Jin, Peter Huang, Jinil Park, J Y. Yoo and Kenneth S. Breuer. Experiments in Fluids, Vol.

37, pp. 825-833, 2004.

Chapter 3. Paper 2. “Direct measurement of slip velocities using three-dimensional total

internal reﬂection velocimetry” by Peter Huang, Jeﬀrey S. Guasto and Kenneth S. Breuer. Journal

of Fluid Mechanics, Vol. 566, pp. 447-464, 2006.

Chapter 4. Paper 3. “Direct measurement of slip length in electrolyte solutions” by Peter

Huang and Kenneth S. Breuer. To be submitted to Physics of Fluids, 2006.

Chapter 5. Paper 4. “Direct measurement of anisotropic near-wall hindered diﬀusion using

total internal reﬂection velocimetry” by Peter Huang and Kenneth S. Breuer. To be submitted to

Physical Review E, 2006.

Chapter 6. Paper 5. “Simulations of hindered diﬀusion in shear ﬂow and its implications for

near-wall velocimetry” by Peter Huang and Kenneth S. Breuer. To be submitted to Physics of

Fluids, 2006.

Chapter 7. Concluding remarks and suggested studies.

iii

I would like to ﬁrst thank my mentor, Professor Kenneth Breuer, for his guidance and support

through my graduate study. Without his encouragement, constructive criticisms and inexhaustible

knowledge, the projects described in this dissertation would not have been fruitful. I also would

like to thank my dissertation readers, Professor Eric Lauga and Professor Anubhav Tripathi, for

their insightful comments during dissertation revisions. Numerous discussions with Professor Tri-

pathi and Professor Thomas Powers during the years on chemistry and statistical mechanics are

acknowledged and very much appreciated.

A special thank goes to my fellow graduate student and my friend Jeﬀrey Guasto. Without

his creative ideas and brilliant suggestions many subtleties of experimental methods and results

would not have been found. I also would like to thank Dr. Songwan Jin, for his introduction of the

total internal reﬂection ﬂuorescent microscopy setup. In addition, I am very grateful to Professor

MinJun Kim, Professor Sylvain Cloutier, Jahn Torres, Teng-Fang Kuo, Brian Burke, Jinkee Lee

and Matt Kerby, for their generous help in micro-fabrication, optical system design and setup,

nano-scale measurements and sharing of lab equipments.

As a lowly ranked graduate student, the administrative and research supports of Mr. Jeﬀrey

Brown, Mr. Michael Jibitsky, Mr. Brian Corkum, Mr. Charles Vicker and Ms. Virginia Novak

are especially appreciated. Without their kind assistance many research projects would not have

moved forward as smoothly as they did.

Finally I would like to thank my parents, my sister and my extended family for their love,

support and best wishes over the years. My greatest gratitude goes to my wife, for her love,

patience and encouragement throughout the years of graduate study, and for putting up with me

during the ups and downs of experiments.

iv

Contents

1 Introduction 1

1.1 BOUNDARY SLIP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.2 HINDERED DIFFUSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.3 TOTAL INTERNAL REFLECTION VELOCIMETRY . . . . . . . . . . . . . . . . 4

1.4 SUBTLETIES OF NEAR-WALL SHEAR FLOW . . . . . . . . . . . . . . . . . . . . 6

2 Paper 1: Near-surface velocimetry using evanescent wave illumination 8

2.1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

2.2 EXPERIMENTAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.3 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

2.3.1 Cross-stream Velocity Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 14

2.3.2 Streamwise Velocity Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2.3.3 Comparisons with Numerical Simulations . . . . . . . . . . . . . . . . . . . . 18

2.4 CONCLUDING REMARKS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3 Paper 2: Direct measurement of slip velocities using three-dimensional total

internal reﬂection velocimetry 22

3.1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

3.2 THEORETICAL CONSIDERATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3.2.1 Total Internal Reﬂection Microscopy . . . . . . . . . . . . . . . . . . . . . . . 23

3.2.2 Emission Intensity of Fluorescent Particles . . . . . . . . . . . . . . . . . . . 24

3.2.3 Near-Surface Shear Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

3.3 EXPERIMENTAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

3.3.1 Materials and Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

3.3.2 Velocimetry Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

3.4 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

3.4.1 Validation of Intensity Calibration Curve . . . . . . . . . . . . . . . . . . . . 31

3.4.2 Hindered Diﬀusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

3.4.3 Velocity Distributions of Particles . . . . . . . . . . . . . . . . . . . . . . . . 32

3.4.4 Measurements of Apparent Slip Velocities . . . . . . . . . . . . . . . . . . . . 34

3.5 CONCLUDING REMARKS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

4 Paper 3: Direct measurement of slip length in electrolyte solutions 39

5 Paper 4: Direct measurement of anisotropic near-wall hindered diﬀusion using

total internal reﬂection velocimetry 43

5.1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

v

5.2 THEORY OF HINDERED DIFFUSION . . . . . . . . . . . . . . . . . . . . . . . . . 44

5.3 EXPERIMENTAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

5.4 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

5.5 SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

6 Paper 5: Simulations of hindered diﬀusion in shear ﬂow and its implications for

near-wall velocimetry 50

6.1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

6.2 THEORIES AND COMPUTATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 51

6.2.1 The Langevin Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

6.2.2 Eﬀects of Shear on Particle Velocities . . . . . . . . . . . . . . . . . . . . . . 53

6.2.3 Hindered Diﬀusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

6.2.4 Implementation of Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

6.3 RESULTS AND DISCUSSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

6.3.1 Sedimentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

6.3.2 Particle Displacement Due to Hindered Diﬀusion . . . . . . . . . . . . . . . . 55

6.3.3 Particle Drop-in’s and Drop-out’s . . . . . . . . . . . . . . . . . . . . . . . . . 58

6.3.4 Horizontal Apparent Velocity Distributions . . . . . . . . . . . . . . . . . . . 60

6.3.5 Time Evolution of Apparent Velocity Distributions . . . . . . . . . . . . . . . 62

6.4 CONCLUDING REMARKS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

7 Concluding Remarks and Suggested Studies 68

A Calibration of beam incident angle 70

B Shear-induced lift force (or more precisely, lack of ) on near-wall submicron-

particles 73

C Evanescent wave image of micron-sized ﬂuorescent particles 75

vi

List of Figures

1.1 Schematic of total internal reﬂection ﬂuorescence microscopy . . . . . . . . . . . . . 5

2.1 Schematic of objective-based TIRFM . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2.2 Schematic of the experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2.3 Particle images of diﬀerent illumination methods: wideﬁeld (direct, ﬂood) illumination 12

2.4 Particle images of diﬀerent illumination methods: near-wall TIRFM image . . . . . . 13

2.5 Schematic of near-wall particles moving near the surface illustrating the observation

range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

2.6 Distribution of particle velocity vectors of 200-nm particles . . . . . . . . . . . . . . 14

2.7 Cross-stream Brownian motion of particles in an inﬁnite medium and near wall . . . 15

2.8 Experimentally-measured distribution of streamwise velocities of 200-nm diameter

particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.9 Apparent particle velocity vs. shear rate . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.10 Streamwise velocity distribution of 200-nm particles determined from Monte Carlo

simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.11 Streamwise apparent velocity predicted by simulation . . . . . . . . . . . . . . . . . 20

3.1 Objective-based total internal reﬂection ﬂuorescence microscopy . . . . . . . . . . . . 24

3.2 The emission intensity distribution of particles in a uniform concentration ﬁeld . . . 25

3.3 The predicted position distribution of particles with 0.5 < I

e

/I

e

0

< 1 in a uniform

concentration ﬁeld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

3.4 The ratio of statistical apparent velocity of particles and mean ﬂuid velocity under

no slip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

3.5 Image acquisition system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

3.6 Fluorescent particle intensity as a function of its distance to the glass surface . . . . 30

3.7 Observed ﬂuorescent particle intensity distribution and its probability density func-

tion (PDF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

3.8 Ratio of hindered diﬀusion coeﬃcients (D

exp

) for Brownian motion parallel to a surface 32

3.9 Distribution of observed particle streamwise velocities under various shear rates . . . 33

3.10 Distribution of observed particle streamwise velocities after scaling . . . . . . . . . . 34

3.11 Experimental apparent velocity of particles in a shear ﬂow over a hydrophilic surface 35

3.12 Experimental apparent velocity of particles in a shear ﬂow over a hydrophobic surface 36

3.13 The additional slip length due to surface hydrophobicity . . . . . . . . . . . . . . . . 36

4.1 Objective-based total internal reﬂection velocimetry (TIRV) system . . . . . . . . . 40

4.2 Measured slip lengths of aqueous solutions . . . . . . . . . . . . . . . . . . . . . . . . 42

5.1 Schematic of total internal reﬂection velocimetry . . . . . . . . . . . . . . . . . . . . 45

vii

5.2 Intensity calibration of 1.5-µm radius ﬂuorescent particles in evanescent ﬁeld . . . . 46

5.3 Hindered diﬀusion correction vs. particle/glass gap size . . . . . . . . . . . . . . . . 47

6.1 A schematic of the simulation geometry . . . . . . . . . . . . . . . . . . . . . . . . . 52

6.2 Sedimentation of large particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

6.3 Sedimentation of small particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

6.4 Particle displacement distribution due to hindered diﬀusion . . . . . . . . . . . . . . 58

6.5 Spatial distribution of small particles due to hindered diﬀusion . . . . . . . . . . . . 59

6.6 Spatial distribution of particles from a ﬁnite layer at various times . . . . . . . . . . 59

6.7 Percentage of particles remaining in imaging range . . . . . . . . . . . . . . . . . . . 60

6.8 Apparent velocity distribution of particles remaining in a ﬁnite imaging range . . . . 61

6.9 Normalized apparent velocity distribution of particles in a ﬁnite imaging range . . . 61

6.10 Apparent velocity distribution of particles from various imaging ranges . . . . . . . . 62

6.11 Collapsed apparent velocity distribution of particles at various imaging range . . . . 63

6.12 Time evolution of apparent velocity distribution . . . . . . . . . . . . . . . . . . . . 63

6.13 Time evolution of mean particle apparent velocity . . . . . . . . . . . . . . . . . . . 64

6.14 Rescaled time evolution of mean particle apparent velocity . . . . . . . . . . . . . . . 65

6.15 Schematic of potential paths for particle translation . . . . . . . . . . . . . . . . . . 66

A.1 Schematic of laser beam refraction at the glass/air interface . . . . . . . . . . . . . . 71

A.2 Photo and schematic of beam incident angle measurement . . . . . . . . . . . . . . . 71

A.3 Plot of laser beam angle vs. converging lens position . . . . . . . . . . . . . . . . . . 72

C.1 Schematic of COMSOL simulation geometry . . . . . . . . . . . . . . . . . . . . . . . 76

C.2 COMSOL simulation of total internal reﬂection . . . . . . . . . . . . . . . . . . . . . 76

C.3 Intensity decay of evanescent ﬁeld . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

C.4 COMSOL simulation of a particle with d/λ = 0.39 in evanescent ﬁeld . . . . . . . . 77

C.5 COMSOL simulation of a particle with d/λ = 6 in evanescent ﬁeld . . . . . . . . . . 78

C.6 COMSOL simulation of a particle with d/λ = 12 in evanescent ﬁeld . . . . . . . . . 78

C.7 Overall evanescent energy in the suspended particles . . . . . . . . . . . . . . . . . . 79

C.8 Cross-sectional intensity proﬁle of a 3-µm particle (d/λ = 6) . . . . . . . . . . . . . . 80

C.9 Digital image of a 3-µm particle (d/λ = 6) in contact with glass surface . . . . . . . 81

C.10 Cross-sectional intensity proﬁle of a 6-µm particle (d/λ = 12) . . . . . . . . . . . . . 82

C.11 Digital image of a 6-µm particle (d/λ = 12) in contact with glass surface . . . . . . . 82

viii

List of Tables

6.1 Sample values of the Peclet number and the sedimentation coeﬃcient . . . . . . . . 53

6.2 Representative values of the non-dimensional time between consecutive image acqui-

sition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

ix

Chapter 1

Introduction

Since the introduction of the ﬁrst microﬂuidic device, these miniaturized ﬂuidic manipulation sys-

tems have been regarded as one of the most promising technologies of the late twentieth century.

In particular, investigations into its application in biotechnology has been the most intense. Exam-

ples of such applications include immunosensors [1], reagent mixing [2], content sorter [3] and drug

delivery [4]. Microﬂuidic devices are very attractive in biotechnology over conventional technology

because they require small sample volume and produce rapid results. Indeed, for chemical reac-

tions whose reaction sites are at solid surfaces, the high surface-area-to-volume-ratio characteristic

of microﬂuidics oﬀers a much higher eﬃciency [5]. On the other hand, the high surface-area-to-

volume-ratio also means that near-surface phenomena will have a much larger inﬂuence on the bulk

of the ﬂuid content, for example the viscous drag on the channel walls. In both cases, understand-

ing of interactions between the ﬂuid content and the solid boundary is critical in designing and

analyzing microﬂuidic devices.

Under most circumstances, the solid boundary is viewed as rigid and inert such that physical

and structural changes due to ﬂuidic forces are nonexistent. Thus the majority of interesting

surface-induced physical phenomena occur in the near-surface region of the ﬂuid phase and can be

categorized into two groups: (1) changes of the ﬂuid mechanical characteristics due to the presence

of the solid surface; (2) interactions between the dissolved molecules, suspended particulates and

the solid surface. Examples of physical phenomena in the former group include electrokinetic ﬂow

[6], slip ﬂow [7] and surface chemistry directed ﬂow [8, 9], while particle or cell adhesion [10] and

detachment [11], increased hydrodynamic drag [12], electrostatic interactions [13] and eﬀects of

depletion layers [14] are eﬀects of the latter group.

1.1 BOUNDARY SLIP

One of the ﬂuid mechanics questions that have remained unanswered over centuries is the slip ﬂow

and its origin. Unlike polymer solutions whose slip behaviors have been thoroughly investigated

[15, 16, 17], the existence of boundary slip in a Newtonian liquid has been a controversial topic. Even

though the idea of a slip ﬂow has been considered by scientists as early as Newton [18], empirical

data up to the late twentieth century had deemed it negligible. The strong experimental support

of such assumption could be due to the fact that the magnitude of slip velocity was much smaller

than the measuring instrument accuracy and thus remained undetectable. Another possibility is

the relatively insigniﬁcant impact of slip on the ﬂuid bulk ﬂow in the macroscopic scale. Westin et

al. [19] calculated that the ratio of slip velocity to bulk velocity becomes very small if the channel

height is more than a few hundred micrometers. Therefore when macroscopic ﬂow measurements

1

2

were conducted slip eﬀect could be hardly noticeable.

In the past decade slip ﬂow began to receive more attention again, because some earlier ex-

periments [20, 21] and molecular dynamics simulations [22, 23, 24] have reported slip boundary

conditions in Newtonian liquid. Since then many experimental attempts were made to conﬁrm the

existence and the magnitude of slip velocities, with varying degrees of accuracy and uncertainty. In

some of these experiments, slip velocity was indirectly inferred from measurement of other physical

quantities. For instance, the relationship between applied pressure drops and measured ﬂow rates

was used by Choi et al. [25] to infer slip velocity, while the forces required to move two surfaces

separated by a thin ﬁlm of the test ﬂuid were employed Zhu & Granick [26], Neto et al. [27] and

Cottin-Bizonne et al. [28] to calculate slip velocities. Others took a direct approach of studying

slip by measuring near-surface ﬂow velocities. Examples of the direct measurements include ﬂuo-

rescence recovery after photobleaching (FRAP) by Pit et al. [29] and micro-scale particle image

velocimetry (µPIV) by Tretheway & Meinhart [30] and Joseph & Tabeling [31].

These experimental studies produced various magnitudes and dependencies of boundary slip.

The commonly used formulation to characterize boundary slip is the slip length, δ, which is based

on the Navier hypothesis that the velocity of a ﬂuid at a solid surface is proportional to the shear

stress. That is,

δ =

U

slip

˙ γ

s

, (1.1)

where U

slip

is the slip velocity and ˙ γ

s

is the ﬂuid shear rate at the solid surface. Experimentally

measured slip lengths were reported to range from micrometers [20, 30, 32], hundreds of nanometers

[29, 33] to less than 100 nanometers [25, 26, 27, 28, 31]. Disagreement also exist on whether the

slip behavior is shear-dependent [21, 25, 26, 27] or shear-independent [20, 28, 29, 31, 32]. Of

particular interest to microﬂuidics is aqueous solution slip over diﬀerent surface conditions as water

is the most common solvent in biological and chemical applications. Although it is generally agreed

among research ﬁndings that surface hydrophobicity aids slip eﬀect [25, 30], again the magnitude

of such an eﬀect remains controversial.

The ability of total internal reﬂection velocimetry (TIRV, to be introduced later) in performing

near-surface measurements makes it a perfect technique for direct observation of slip velocities in a

shear ﬂow. In Paper 1: Near-surface velocimetry using evanescent wave illumination (chapter 2), we

report on our ﬁrst attempt to measure slip velocities of deionized water using the TIRV technique.

In this report, it is shown that velocities of ﬂuid elements within a few hundred nanometers from

a solid surface can be accurately measured, demonstrating the potential of the TIRV technique in

making direct measurements of slip velocities. Although a quantitative conclusion of slip length

magnitude could not be drawn due to the uncertainty in determination of the exact imaging range,

a qualitative conclusion is reached that surface slip length of an aqueous solution would be small

and surface chemistry-dependent, and a slip length above a few hundred nanometers is unlikely.

The accuracy of slip measurements is further improved with the implementation of three-

dimensional tracking in the TIRV technique. In Paper 2: Direct measurement of slip velocities

using three-dimensional total internal reﬂection velocimetry (chapter 3), we report on a slip length

of deionized water being less than 100 nm, and an additional slip length of 16 nm is found at-

tributable to surface hydrophobicity. In conducting this experiment, several physical factors that

are suspected of inducing slip are also examined. With measurements conducted at glass sur-

faces of sub-nanometer surface roughness, the obtained slip length values agree with the surface-

roughness dependency previously reported by Granick et al. [34] The issue of apparent slip caused

by nano-bubbles at the glass surface is additionally disputed with experiments conducted with

sub-nanometer surface roughness and degassed test ﬂuids.

3

Still, questions remained on whether other physical forces, particularly the electrostatic and

electrokinetic eﬀects proposed by Lauga et al. [7, 35], would lead to false slip results in TIRV mea-

surements. We address such a concern in Paper 3: Direct measurement of slip length in electrolyte

solutions (chapter 4), by repeating the slip measurements with electrolyte solutions whose ionic

concentrations have been predicted to reduce the apparent slip eﬀect to sub-molecular level. It is

observed that the presence of electrolytes has no eﬀect on the measured slip lengths, suggesting

that the observed slip velocities are most likely not due to electrostatic and electrokinetic eﬀects,

but are consequences of true boundary slip.

1.2 HINDERED DIFFUSION

Another near-surface phenomenon with great ﬂuid mechanical and mass transport implications is

hindered diﬀusion of colloidal particles. The concept of near-wall hindered diﬀusion stems from an

increased frictional coeﬃcient on a near-wall object. Einstein proposed that the diﬀusion coeﬃcient

of a colloidal object is the ratio of the ﬂuid thermal energy to the object’s frictional coeﬃcient in

Stokes ﬂow. Thus if a particle experiences an increase in ﬂuidic friction as it approaches a solid

wall, its diﬀusive translation or Brownian motion will be hindered. Brenner [36] and Goldman et al.

[37, 38] were the ﬁrst to analytically solve the increased frictional coeﬃcients of a near-wall sphere

with a lubrication formulation. Their results were later re-conﬁrmed by Chaoui & Feuillebois [12]

with an spherical harmonics expansion method.

Besides being a ﬂuid mechanics theory, hindered diﬀusion has additional implications in chemical

engineering and drug delivery systems since diﬀusion is the dominant mass transport mechanism

in microﬂuidics. Because of its signiﬁcance, advancement of near-surface measurement techniques

had lead to several experimental studies of hindered diﬀusion. Employed experimental techniques

include evanescent light scattering oﬀ freely suspended particles by Bevan & Prieve [39], evanescent

light-scattering spectroscopy by Hosoda et al. [40], catch-and-release video microscopy with optical

tweezers by Lin et al. [41], evanescent light scattering coupled with optical radiation pressure

by Oetama & Walz [42] and three-dimensional ratiometric total internal reﬂection ﬂuorescence

microscopy with nanoparticles by Banerjee & Kihm [43]. Most of these studies have reported

hindered diﬀusion coeﬃcients agreeing to values derived from the theories of Brenner and Goldman

et al.

In the theories of Brenner and Goldman et al., the increased friction factor is a function of

particle radius and gap size between the particle and the solid wall. Unlike in the ﬂuid bulk,

the ﬂuidic friction also becomes anisotropic in the near-wall region. In other words, the hindered

diﬀusion coeﬃcient is diﬀerent for directions normal and parallel to the solid surface. Few studies

have attempted to measure such anisotropicity simultaneously due to experimental limitations. Lin

et al. [41] demonstrated such anisotropicity for particles whose gap-size-to-radius ratio is greater

than one, and found hindered diﬀusion coeﬃcient values agreeing with theories. Another study

that reported anisotropic hindered diﬀusion coeﬃcients for gap-size-to-radius ratio greater than

one was conducted by Banerjee & Kihm [44]. However, their study reported that the measured

diﬀusion coeﬃcient in the direction normal to the solid wall agreed with the theoretical values only

when large particles were tested.

By applying the 3D-TIRV technique to freely suspended micron-sized ﬂuorescent particles, we

aim to simultaneously observe the three-dimensional anisotropic hindered diﬀusion for gap-size-to-

radius ratio much less than one. The theory under this condition is vastly diﬀerent from that of the

gap-size-to-radius ratio greater than one, and based on our literature survey no such experimen-

tal conﬁrmation of the theory has been reported. In Paper 4: Direct measurement of anisotropic

4

near-wall hindered diﬀusion using total internal reﬂection velocimetry (chapter 5), we demonstrate

that the three-dimensional tracking technique of TIRV can be adopted into 3D displacement mea-

surements of freely suspended 1.5-µm radius particles. The displacement measurements reveal that

the hindered diﬀusion coeﬃcients are in close agreement with the theoretical values predicted by

the asymptotic solutions of Brenner and Goldman et al. for gap-size-to-radius ratio much less than

one, and hindered diﬀusion anisotropicity is simultaneously demonstrated in all data sets.

1.3 TOTAL INTERNAL REFLECTION VELOCIMETRY

With so much interest in near-surface phenomena, researchers have developed various techniques

to study them. Optical microscopy has been widely used to observe interactions in the micrometer

scale. However, as fabrication technology advances, the deﬁnition of “near-surface” has also evolved

from microscopic and to the nano-scale. Traditional optical techniques are no longer suﬃcient now

because the visible wavelength is the physical limit of optical resolution (∼ 0.5 µm). A frequently

used technique to overcome this obstacle is evanescent wave imaging [45]. In this technique, a beam

of collimated laser light is brought to a solid/liquid interface through the solid phase at a large

incident angle, as shown in ﬁgure 1.1. Since solids typically have higher indices of refraction than

ﬂuids do, total internal reﬂection occurs at the interface if the incident angle is greater than the

critical angle predicted by Snell’s Law. In fact, at the nano-scale this reﬂection is not “total”, but

a small fraction of energy, called evanescent waves, extends into the ﬂuid phase. In the ﬂuid phase

the evanescent wave energy or intensity, I, decays exponentially with distance, z, away from the

two-medium interface by

I(z) = I

0

e

−z/p

, (1.2)

where I

0

is the intensity at the interface and p is known as the evanescent wave penetration depth.

The penetration depth, which characterizes the length scale of the evanescent ﬁeld, can be calculated

from

p =

λ

0

4π

_

n

2

s

sin

2

θ −n

2

l

_

−

1

2

, (1.3)

where λ

0

is the wavelength of the incident light, θ is the beam incident angle and n

s

and n

l

are

the refractive indices of the solid and liquid, respectively. For visible light, the evanescent wave

energy decays to zero within a few hundred nanometers. Thus by using the evanescent wave as

an illumination source, one can observe dynamics of ﬂuids and suspended particulates within a

few hundred nanometers from the solid surface, while contents outside of this layer would remain

invisible. Consequently near-surface phenomena can be observed with clarity and without the

interfering noise contributed from objects in the ﬂuid bulk.

Since the 1970’s, biologists have combined ﬂuorescence and evanescent wave imaging in studying

near-surface biological events [46, 47]. Termed “total internal reﬂection ﬂuorescence microscopy”

(TIRFM), this technique allows observation of ﬂuorescently labelled samples placed in the evanes-

cent ﬁeld and under a high magniﬁcation microscope. Fluorescence is a quantum optical eﬀect

of a unique group of molecules called ﬂuorophores, whose quantum states can be excited by a

speciﬁc range of visible light and release photons of a longer wavelength after initial excitation.

Their molecular sizes are excellent for probing near-surface regions at the nano-scale. Examples of

TIRFM include the previously mentioned ﬂuorescent recovery after photobleaching (FRAP) and

ﬂuorescence resonance energy transfer (FRET). In FRAP, the ﬂuorophores of a chosen spot in-

side the microscope ﬁeld of view is purposely photobleached with a high power laser beam. The

light-emitting ﬂuorophores in the surrounding area will diﬀuse into this “dark” spot immediately

following the photobleaching. By measuring the diﬀusivity of these light-emitting ﬂuorophores, one

5

θ

z

liquid

solid

~ penetration depth

Figure 1.1: Schematic of total internal reﬂection ﬂuorescence microscopy (TIRFM). A ﬂuorescent

particle suspended in water was placed in an evanescent ﬁeld. If the illumination beam incident

angle, θ, is greater than the critical angle predicted by Snell’s law, total internal reﬂection occurs

at the solid/liquid interface. The evanescent energy then illuminates the encapsulated ﬂuorophores

inside the particle.

can study the targeted molecule mobility. For instance, FRAP has been reported in measurement

of protein mobility and activity in living cells [48]. FRET, on the other hand, takes advantages

of a quantum energy transfer that occurs between matched ﬂuorescent molecules of two diﬀerent

wavelengths [49]. Because such energy transfer can only occur if the two molecules are less than

10 nm apart, they oﬀer an opportunity to examine interactions in the molecular level.

Surprisingly, a long time had passed before physical scientists ﬁnally caught up with the merits

of evanescent wave imaging. At ﬁrst, evanescent energy scattered oﬀ non-ﬂuorescent suspended

particles was used in quantitative measurements of near-surface dynamics. Such experimental

studies include measurement of surface charge densities on suspended particles by von Grunberg

et al. [50], quantifying double-layer repulsion between a colloidal particle and a glass substrate by

Flicker et al. [51], eﬀects of particle size on near-wall particle depletion by Kok et al. [14], charged

particle adsorption by Kun & Fendler [52], and hindered diﬀusion by Bevan & Prieve [39]. Only in

the past decade were ﬂuorescent tracer particles used in microscopic dynamics measurements.

Particle-based velocimetry has long been used in ﬂuid visualization and measurement [53]. It

is based on an intuitive and for most part correct assumption that the seeding tracer particles are

carried by the ﬂuid surrounding them, and therefore their translational velocities must be that of the

local ﬂuid elements. Apparent velocities of the tracer particles are calculated based on displacements

of the tracer particles and the time between successive particle imaging. When particle-based

velocimetry methods were adopted to study microﬂuidics, sub-micron ﬂuorescent tracer particles

were used to minimize light scattering and imaging noise while attaining spatial resolutions of

tens of nanometers [54]. Santiago et al. [55] were the ﬁrst to demonstrate a correlation-based

microscopic particle image velocimetry (µPIV) to map out a velocity ﬁeld around a Hele-Shaw cell.

In their experiment, cross-correlation analysis was performed on successive images of ﬂuorescent

tracer particles to identify the most probable ensemble displacements. Since their report, µPIV

has been the work horse among diagnostic techniques of microﬂuidics.

When applying to near-surface measurements, µPIV does suﬀer a major drawback. Its resolu-

tion in the direction perpendicular to the imaging focal plane is limited by the focal depth of the

6

microscope objective lens and is at least 0.5 µm [31]. Consequently, µPIV could not distinguish

physical features within 0.5 µm from a solid surface. Zettner & Yoda [56] overcame µPIV’s deﬁ-

ciency by combining it with evanescent wave illumination. The short eﬀective range of evanescent

wave allowed them to measure ﬂuid velocities that were within 280 nm from a solid surface. Li

et al. [57] further extended this nano-PIV technique into a multilayer correlation analysis, where

quantitative measurement can be performed on events that occur within 100 nm from the surface.

Zettner & Yoda’s nano-PIV is undoubtedly a novel technique. However it still has two signiﬁcant

limitations. Firstly, rapid Brownian motions of nanoparticles could lead to a large amount of particle

“drop-in” and “drop-out”, or events where particles diﬀuse in and out of the evanescent ﬁeld between

consecutive frames. Since the statistical analysis of nano-PIV does not make an attempt to treat the

drop-in’s and drop-out’s, signiﬁcant measurement errors could persist. Secondly, because diﬀusion

is treated as measurement noise in the cross-correlation analysis of the nano-PIV, it is unsuitable

if diﬀusive dynamics is of interest.

In Paper 1: Near-surface velocimetry using evanescent wave illumination (chapter 2), we present

a technique, called “total internal reﬂection velocimetry” (TIRV), as an alternative to nano-PIV

in near-surface measurements. By combining TIRFM with tracking of individual tracer particle,

Brownian motions of the particle ensemble can be monitored and statistically analyzed, leading

to a more accurate accounting of all contributing particles. In Paper 2: Direct measurement of

slip velocities using three-dimensional total internal reﬂection velocimetry (chapter 3), we extend

the TIRV technique to three-dimensional, further improving its accuracy and applicability. It is

observed that the peak intensity of a ﬂuorescent particle decays exponentially in the same length

scale as the evanescent wave energy, and thus a particle’s peak intensity can be used to infer its

distance from the solid surface.

As mentioned previously, we use the TIRV technique to measure aqueous solution boundary

slip and near-surface hindered diﬀusion of spherical particles. In Paper 2: Direct measurement

of slip velocities using three-dimensional total internal reﬂection velocimetry (chapter 3) and in

Paper 3: Direct measurement of slip length in electrolyte solutions (chapter 4), 100- and 200-nm

radius ﬂuorescent particles are employed in 3D-TIRV experiments to measure slip lengths over

hydrophilic and hydrophobic surfaces. The analysis of the image data reveals that a statistical

approach is needed in making near-surface velocimetry measurement even for particles whose size

variation is as small as a few percent, owing to the sensitivity of evanescent wave imaging. In Paper

4: Direct measurement of anisotropic near-wall hindered diﬀusion using total internal reﬂection

velocimetry (chapter 5), the TIRV technique is extended to observing anisotropic near-wall hindered

diﬀusion of 1.5-µm radius ﬂuorescent particles. Under evanescent wave imaging, the peak intensity

of these large particles follow an exponential decay relation that is also identical to the exponential

decay of evanescent energy, and thus the same three-dimensional particle tracking principle applies.

Both slip and hindered diﬀusion studies demonstrate the applicability and versatility of the TIRV

technique in making near-wall particle velocity and displacement measurements.

1.4 SUBTLETIES OF NEAR-WALL SHEAR FLOW

As previous discussion have emphasized, Brownian motion of particles in the near-surface region is a

non-negligible mechanism and has signiﬁcant implications in the accuracy of near-wall velocimetry.

Many of the issues that need to be considered, however, could not be easily assessed through

experimental data. Thus numerical approaches oﬀer insightful alternatives to explore the subtleties

of near-wall ﬂow.

The main concern in near-wall velocimetry is the ensemble behavior of tracer particles in the

7

time interval between consecutive image acquisitions, and more importantly, how such ensemble

behavior aﬀects the accuracy of velocity measurements. Two equally viable numerical approaches

have been proposed to study Brownian motion-related problems [58]. In the Fokker-Planck ap-

proach, the time evolution of the particle ensemble phase space conﬁguration function is computed

through numerical solution of the momentum-position partial diﬀerential equations. The ensemble

behaviors are then obtained from probability analysis using the phase space conﬁguration function.

Recently, Sadr et al. [59] had taken the Fokker-Planck approach to study the diﬀusion-induced bias

in near-wall velocimetry.

The other approach takes advantage of the Langevin equation in which the displacement of

a particle consists of a deterministic component (such as displacement of the suspending ﬂuid)

and a stochastic component (such as Brownian motion). With a proper time step size, initial and

boundary conditions, ensemble behavior of particles can be obtained through statistical analysis of

a large number of repeated simulations. Also called Brownian Dynamics (BD) simulations for its

direct emulation of Brownian motions, this approach has been used in studying the binding rates

between attached molecules [60], colloidal particle deposition in a microchannel ﬂow [61], accuracy

of potential energy proﬁles determined by evanescent wave scattering [62] and the accuracy of

nano-PIV [63]. Its intuitive resemblance to a physical velocimetry experiment has gained some

popularity in colloidal studies.

We are most interested in the ensemble behaviors of near-surface particles in a shear ﬂow, and

the eﬀects of the wall presence and hindered diﬀusion on the measured velocities because these

are issues that we have noticed during our TIRV measurements of boundary slip and anisotropic

hindered diﬀusion. In Paper 5: Simulations of hindered diﬀusion in shear ﬂow and its implications

for near-wall velocimetry (chapter 6), the relative strengths of near-wall shear and diﬀusive forces

are explored through Brownian dynamics simulations. It is observed that the shear force dominates

over diﬀusion at Pe > 3. In addition, asymmetric shape and width of apparent velocity distributions

are attributed to the shear eﬀect, and we believe it can lead to signiﬁcant inaccuracy in nano-PIV

if not treated appropriately.

The same Brownian dynamics simulation also provides a tool to assess the eﬀects of hindered

diﬀusion and wall presence on various near-wall velocimetry techniques. With diﬀusive time and

particle radius as time and length scales, respectively, it is found that if the time interval between

successive particle image acquisitions is short, hindered diﬀusion causes an under-estimation of

ﬂuid velocity due to biased sampling of tracer particles very close to the wall. However, if the

time interval between successive particle image acquisitions is long, a signiﬁcant portion of the

tracer particles would sample planes of higher velocities, resulting in an over-estimation of overall

ﬂuid velocity. Particle drop-in’s and drop-out’s, are found to be a potential source of measurement

error for nano-PIV because of the rapid Brownian motion of nanoparticles. The combined eﬀect of

the observations described above is that near-wall particle-based velocimetry measurement is not

time-invariant. Still, the results found in the Brownian dynamics simulation oﬀer a way where the

true ﬂuidic velocities can be inferred from particle apparent velocities through proper scaling. This

scaling method, however, is available only for TIRV but not for nano-PIV, making TIRV the more

superior method in near-surface measurements.

Chapter 2

Paper 1: Near-surface velocimetry

using evanescent wave illumination

Total Internal Reﬂection Velocimetry (TIRV) is used to measure particle motion in the near-wall

region of a microﬂuidic system. TIRV images are illuminated with the evanescent ﬁeld of an

incident laser pulse and contain only particles that are very close to channel surface. Sub-micron

sized ﬂuorescent particles suspended in water are used as seed particles and their images are analyzed

with a PTV algorithm to extract information about apparent slip velocity. At relatively low shear

rates (less than 2500 sec

−1

), a velocity, proportional to the shear rate was observed. The statistical

diﬀerence between velocities measured over hydrophilic and hydrophobic surfaces was found to be

minimal. The results suggest that the slip length, if present, is less than 25 nm, but uncertainty

regarding the exact character of the illumination ﬁeld prevents a more accurate measurement at this

time. Numerical simulations are presented to help understand the results and to provide insight into

the mechanisms that result in the experimentally observed distributions. Issues associated with the

accuracy of the experimental technique and the interpretations of the experimental results are also

discussed.

2.1 INTRODUCTION

Over the past few years, studies regarding near-wall ﬂuid motion have intensiﬁed because of the

emergence of micro-electro-mechanical-systems (MEMS), where the ﬂuid-surface interaction is im-

portant to the design, fabrication and performance of these devices. In particular, the no-slip

boundary condition, which has long been experimentally veriﬁed in macroscopic ﬂow, now receives

a great amount of attention in microﬂuidics. Moreover, many biological applications of microﬂu-

idic devices require surface coatings that change the wetting ability of aqueous or biological ﬂuids.

Thus, a better understanding of ﬂuid-surface interaction becomes necessary in designing applicable

devices.

Many experimental techniques have been applied to study the eﬀect of slip on both hydrophilic

and hydrophobic surfaces. In general, slip measurement techniques can be classiﬁed into indirect

and direct methods. In the indirect methods, slip velocity is inferred from other measurements, for

example, the ﬂow rate and pressure within the ﬂow duct [20, 21, 25], or from forces required to move

the surfaces [64]. Examples of the direct measurement methods include hot ﬁlm anemometry [32],

total internal reﬂection-ﬂuorescence recovery after photobleaching (FRAP) [29] and micro-PIV [30].

There are also other groups of researchers who attempted to understand the slip phenomenon from

8

9

a theoretical perspective through molecular dynamics simulations [22, 23, 24]. The results from

these studies are quite diverse, and “apparent slip” lengths ranging from nanometers to microns

have been reported. Similarly, the dependence of the slip on the applied shear rate is also a matter

of debate with some results suggesting a constant slip length, while others reporting a slip length

dependent on shear rate and/or surface hydrophobicity.

Recently, a novel technique termed total internal reﬂection ﬂuorescence microscopy (TIRFM)

has been applied to near-wall ﬂuid measurements. The TIRFM technique has long been used in

biological studies, such as cell-substrate contacts, vesicle fusion and single-molecule observation

[65, 66, 67]. It takes advantage of the fact that total internal reﬂection occurs when light travels

from a dense medium (such as a glass cover slip) with refractive index n

1

into a less dense medium

(such as the sample ﬂuid) with refractive index n

2

. Total internal reﬂection occurs if the incident

angle is larger than the critical angle θ

c

= sin

−1

(n

2

/n

1

), which can be derived from Snell’s Law.

When total internal reﬂection occurs, some fraction of the light energy penetrates into the less dense

medium and propagates parallel to the surface. This parallel light wave is known as the “evanescent

wave”. One characteristic of the evanescent wave is that its intensity, I, decays exponentially with

respect to the distance from the two-media interface. Thus, images taken under evanescent wave

illumination have low background noise, showing clear features of sample structure that is near the

interface. There have also been several recent experimental studies of ﬂuid mechanics by applying

evanescent wave illumination [29, 56, 68]. In particular, Zettner and Yoda [56] used the PIV

technique combined with evanescent wave illumination to measure near-surface velocity ﬁeld in

rotating Couette ﬂow.

In this paper, we describe the Total Internal Reﬂection Velocimetry (TIRV) technique, in which

the TIRFM technique is applied to observe particle motion in the close vicinity of microchannel

walls with diﬀerent surface wetting properties. A particle tracking velocimetry (PTV) technique is

applied to track particle displacements and ﬂow velocities near the wall.

2.2 EXPERIMENTAL PROCEDURES

TIRFM requires the creation of total internal reﬂection of a laser beam at the glass-sample interface,

and the presence of ﬂuorescent molecules or particles suspended in the sample ﬂuid for imaging

and measurement. Two diﬀerent optical conﬁgurations are commonly used to create an evanescent

ﬁeld close to the glass-sample interface. The ﬁrst method utilizes a prism to guide the laser beam

into the glass cover slip, which then serves as a waveguide, allowing total internal reﬂection to

occur. The other method, which is prismless, has the illuminating laser beam directed through a

high numerical aperture (NA) microscope objective at an angle that creates total internal reﬂection

at the glass-sample interface, as shown in Fig. 2.1. The maximum incident angle which can be

achieved by using an objective lens is given by

θ

max

= sin

−1

(NA/n

glass

) . (2.1)

As mentioned before, the intensity of an evanescent wave decays exponentially with distance z

away from the two-media interface

I(z) = I

0

e

−z/d

, (2.2)

where I

0

is the light intensity at the interface and d is known as the evanescent wave penetration

depth. The penetration depth, which characterizes the evanescent ﬁeld, can be calculated as:

d =

λ

0

4π

_

n

2

1

sin

2

θ −n

2

2

_

−

1

2

, (2.3)

10

~ Penetration depth

Fluorescent particle solution

Objective lens

Immersion oil

Glass (n = 1.51)

θ

Water (n = 1.33)

z

x

U

Figure 2.1: Schematic of objective-based TIRFM.

where λ

0

is the wavelength of the incident light and n

1

and n

2

are the indices of refraction for glass

and water, respectively. Based on these calculations, one can choose appropriate laser wavelength

and microscope objective or prism to achieve desired penetration depth.

In the present experiment, illustrated in Fig. 2.2, we have adopted the prismless TIRFM

method. A dual head Quantel Brilliant Q-Switched Nd:YAG laser was used to generate a pair

of 532 nm, 5 nsec laser pulses to illuminate the ﬂow. The laser heads were timed to ﬁre with a

pre-determined pulse separation (1.1 to 3.3 ms, depending on shear rate), illuminating two images

for use in a Particle Tracking Velocimetry (PTV) analysis. The beams were focused oﬀ-axis at the

back focal plane of a Nikon PL Apo NA 1.4 100X oil immersion objective lens mounted on a Nikon

Eclipse TE200 inverted epi-ﬂuorescent microscope. Because the laser beam is focused oﬀ-axis, the

beam incident angle at the glass-ﬂuid interface can be controlled by changing the radial location

of the laser beam. With water as the sample ﬂuid, the experimental setup had a critical angle

θ

c

= 61.9

◦

. At incident angles equal to or larger than θ

c

, the laser beam could be totally reﬂected

oﬀ the water-glass interface, creating an evanescent wave ﬁeld. With a water-glass interface, λ

0

=

532 nm and NA = 1.4, it can be calculated that the penetration depth is approximately 150 nm

when the incident angle is θ = 63.4

◦

.

The test cell consisted of a precision glass cover slip on which a polydimethylsiloxane (PDMS)

microchannel was attached. The PDMS channels were fabricated using standard “soft lithography”

techniques [69] and measured 31±1 µm deep, 250±1 µm wide and 25 mm long. They were bonded

to the test surface after exposure to an oxygen plasma which renders both the glass and PDMS

surfaces highly hydrophilic for a short time during which they bond on contact. Following bonding,

the channels were immersed in deionized-water to maintain their hydrophilic surface characteristics.

To create hydrophobic microchannels, it is necessary to coat the glass surface with a transparent

and hydrophobic substance because glass is naturally hydrophilic. We coated glass by immersing

glass into a 5-mM octadecyltrichorosilane (OTS) solution (dissolved in hexadecane) at room tem-

perature for several hours. A self-assembled monolayer (SAM) of OTS formed on the glass surface,

and was made permanent after the glass was rinsed in hexane and ethanol, dried in nitrogen, and

baked at 100

◦

C on a hotplate for a few hours. The coating process was performed in a nitrogen gas

chamber to avoid bulk polymerization. The coated glass was bonded to a cleaned, patterned PDMS

channel to create a hydrophobic microchannel. It has been reported that surface roughness can

11

ICCD

Nd-YAG laser

532 nm

Syringe pump

100X, NA = 1.4

Objective lens

Dichroic mirror and

Barrier filter

PDMS channel

Convex lens

Pulse generator Computer

1360 x 1036 x 12 bit

532 nm, 5 nsec pulse

1.1 - 3.3 ms separation

Figure 2.2: Schematic of the experimental setup.

strongly inhibit boundary slip by transferring momentum if liquid molecules are trapped inside the

holes of the monolayer [29]. Thus, an atomic force microscope (AFM) measurement of glass surface

roughness was also performed. The polished Pyrex glass wafer was measured to have a surface

RMS roughness of 2 nm, while the same wafer had a surface roughness of 4 nm after OTS-coating.

Monodisperse Fluorescent Polymer Microspheres (Duke Scientiﬁc) with diameters of 200 nm

(±5%) and 300 nm (±3%), suspended in pure water at 0.02% and 0.04% volume fractions respec-

tively, were used as seed particles in this experiment. These microspheres have a peak absorption

wavelength of 542 nm and emit a red visible light at 612 nm. Particle solutions were ﬂowed through

the test channels using a Harvard Apparatus 22 syringe pump, at ﬂow rates ranging from 0.6 to

6.0 µL/min (±0.35%). An air gap between the piston and the ﬂuid in the syringe and long tubes

were used to dampen pulsations from the syringe motion. Near-wall particle images were projected

onto a Q-Imaging Intensiﬁed Retiga CCD camera, which has a capacity of recording 1360-pixels-

by-1036-pixels 12-bit images. Under 100X magniﬁcation, each image pixel corresponds to 64.3 nm

in the ﬂow channel and the diﬀraction-limited spot size is 30.9 µm [70]. For 200- and 300-nm

particles, the image diameters are 36.8 and 43.1 µm, respectively [55]. Typically 200 image pairs

were recorded for each ﬂow condition. The recorded image pair was ﬁnally analyzed with a PTV

algorithm written in our group using the MATLAB programming environment. The choice of Par-

ticle Tracking Velocimetry (PTV), rather than Particle Image Velocimetry (PIV) is an important

one and this will be re-addressed later on.

Measurements were taken at several shear rates. For the results presented here, the shear

rate was estimated from the applied volume ﬂow rate, Q, assuming steady laminar ﬂow of an

incompressible ﬂuid between two parallel plates without wall slip

˙ γ

wall

=

_

du

dy

_

wall

=

6Q

h

2

w

, (2.4)

12

Figure 2.3: Particle images of diﬀerent illumination methods: wideﬁeld (direct, ﬂood) illumination.

where h is the channel depth and w is the channel width. If there is signiﬁcant slip at the wall, the

shear rate could be slightly lower than is estimated here [25]. However, for the current experiments,

any possible slip velocity is so small that this uncertainty can be neglected (this presumption will

be conﬁrmed by the results in the following section).

2.3 RESULTS AND DISCUSSION

Figures 2.3 and 2.4 compare particle images of wideﬁeld (direct, ﬂood) illumination and evanescent

ﬁeld illumination. A large amount of background noise is observed in the case of direct illumina-

tion. Such background noise is attributed to the light emitting from the out-of-focus particles in

the bulk of the ﬂuid and such images are common in micro-PIV measurements but lead to poor

cross-correlations during PIV analysis. Evanescent ﬁeld illumination, on the other hand, eliminates

much of the background noise because the evanescent light penetration depth is restricted to ap-

proximately 150 nanometers, and particles in the bulk ﬂuid are not illuminated. This characteristic

allows easy detection of only particles that are close to the channel surface.

To measure particle velocities near the channel surface, several hundred image pairs at various

low shear rates were taken for subsequent PTV image analysis. Bright particles with intensities

above a pre-determined threshold value were identiﬁed in each image. In this study, the intensity

threshold was set at 50% of the brightest particle intensity (usually about 1500-2000 counts from

a 12 bit CCD camera). This threshold value allowed us to detect almost every particle which can

be identiﬁed with the naked eye and restricts the analysis to particles that are well within the

evanescent ﬁeld and in focus. The number of particles identiﬁed in one image is not very sensitive

to the exact threshold value. Typically about 10-20 particles were identiﬁed in each image, although

approximately 50% of these were not tracked between images due to out-of-plane diﬀusion which

causes particles to enter and leave the observation region.

It is important to point out that the determination of an intensity threshold sets an observation

range, as illustrated in Fig. 2.5. The lower bound of the observation range is the particle radius,

13

Figure 2.4: Particle images of diﬀerent illumination methods: near-wall TIRFM image.

Glass Cover Slip

Fluid Velocity

Observation

Range

Figure 2.5: Schematic of near-wall particles moving near the surface illustrating the observation

range.

representing a particle in contact with the channel surface. As the particle moves farther from the

wall, and hence into a region of lower illumination intensity, the emitted intensity also falls. Thus,

the intensity threshold chosen sets an upper bound on the observation range which is diﬀerent from

the penetration depth of the evanescent ﬁeld. The exact size of the observation range was not

known in these experiments and this uncertainty turned out to be the major source of uncertainty

in these experiments and is discussed later on.

Although tracking the particle displacements in the x-y plane (parallel to the surface) was

straightforward, tracking the particles motion in the z -axis (normal to the surface) is not easy.

Ovryn [71] developed a method to determine the three-dimensional position of a spherical particle,

based on resolving the spatial variations in the scattering pattern. However in the evanescent ﬁeld,

illumination intensity varies exponentially with distance from the wall (as shown in Eq. 2.2), and

consequently it is not easy to directly quantitatively associate the ﬂuorescent scattering of a particle

in a non-uniform illumination ﬁeld with the particle’s distance from the wall. For this reason we

14

100 50 0 50 100

40

20

0

20

40

60

80

100

120

140

Cross-stream velocity (μm/sec)

S

t

r

e

a

m

w

i

s

e

v

e

o

c

i

t

y

(

μ

m

/

s

e

c

)

Figure 2.6: Distribution of particle velocity vectors of 200-nm particles with ˙ γ = 469 sec

−1

.

did not attempt to track the particle’s motion normal to the surface. There is no reason why this

should not be possible in the future.

The intensities of pixels surrounding the peak intensity were ﬁtted to a two-dimensional Gaus-

sian curve [72, 73, 74]. Because the particles are known to be spherical with diameter standard

deviation less than 5%, a two-dimensional Gaussian curve ﬁt closely approximates the Lommel func-

tion, and allowed us to locate the particle center coordinates with sub-pixel resolution. Particles

were matched between images using a custom particle tracking algorithm and displacement vectors

were calculated from the displacements of particle centers. A threshold displacement was imposed

to detect error vectors, which were deﬁned as displacements larger than deemed reasonable. These

large displacement vectors usually result from matching two diﬀerent particles mistakenly. At each

testing condition, the total number of validated displacement vectors ranged from 700 to 1500. Us-

ing the geometric scale and the applied pulse separation, a velocity vector can be calculated from

each displacement vector. Figure 2.6 shows an example of a collection of velocity vectors obtained

for a single shear rate. The Brownian motion is particularly strong due to the particle’s small size.

2.3.1 Cross-stream Velocity Analysis

Analysis of the displacements of particles in the cross-stream direction was used as to check the

consistency of the experiment results. In this direction, in the absence of any mean ﬂow, one would

expect that the particle motion would be purely driven by thermal ﬂuctuations. Indeed, we found

that the distributions of spanwise velocities had a Gaussian distribution with mean and skewness

close to zero. The width of the particle displacement distribution, σ, was used to compute the local

diﬀusion coeﬃcient, D:

D =

σ

2

∆t

2

, (2.5)

15

0 500 1000 1500 2000 2500

0

0.5

1

1.5

2

2.5

x 10

13

Shear rate (1/sec)

D

i

f

f

.

C

o

e

f

f

.

x

R

a

d

i

u

s

(

c

m

3

/

s

e

c

)

Figure 2.7: Cross-stream Brownian motion of particles in an inﬁnite medium and near wall (ex-

periment). Solid symbol represents 200-nm particles and open symbol represents 300-nm particles

(, hydrophilic surface; ♦, hydrophobic surface). The dashed line denotes particle diﬀusion in an

inﬁnite medium calculated on the basis of the Stokes-Einstein relation.

and Fig. 2.7 shows the cross-stream diﬀusion coeﬃcient obtained for 200-nm (solid symbol) and

300-nm (open symbol) particles at a variety of diﬀerent streamwise shear rates over both hydrophilic

and hydrophobic surfaces. The diﬀusion coeﬃcient is scaled by the particle radius, r, and the dotted

lines represent scaled particle diﬀusion in an inﬁnite medium calculated based on the Stokes-Einstein

relation:

D

0

r =

k

B

T

6πη

, (2.6)

where D

0

is the Stokes-Einstein diﬀusion coeﬃcient, k

B

is the Boltzmann constant, T is the medium

temperature, and η is the ﬂuid viscosity. As expected, the measured spanwise diﬀusion coeﬃcients

are independent of the streamwise shear rate and the diﬀusion coeﬃcient, when appropriately

scaled, is independent of particle radius. However, as indicated by the dotted line in Fig. 2.7,

the measured values for D are approximately 30% that of the bulk diﬀusion expected. This is

conﬁrmation of the presence of hindered diﬀusion of particles near a solid surface [37, 38]. If we use

the observed value of D with the theory for hindered diﬀusion [37, 38] to calculate the ”apparent

particle distance” from the wall, deﬁned as the distance between the particle center and the wall, we

ﬁnd it to be 110 nm for the 200-nm particles and 165 nm for the 300-nm particles. This is consistent

with the high intensity threshold chosen which deﬁnes a small observation range. Unfortunately,

since we did not carefully monitor the observation range, a more precise estimate is not available

for this data.

2.3.2 Streamwise Velocity Analysis

Figure 2.8 shows an example of the distribution of the streamwise velocities, found by projecting the

velocity distributions onto the mean ﬂow direction. Several features are worth noting. Firstly, the

location of the peak of the distribution increases with increasing shear rate, as one would expect.

16

200 0 200 400 600 800

0

0.01

0.02

Velocity ( μm/sec)

P

D

F

234 (1/sec)

1172 (1/sec)

2344 (1/sec)

Figure 2.8: Experimentally-measured distribution of streamwise velocities of 200-nm diameter par-

ticles over a range of shear rates.

Less expected, and in contrast to the distributions for the spanwise velocities, is the observation

that the distribution widens with increasing shear rate, and that the skewness clearly shifts from

0.15 at the low shear rate (barely noticeable) to a clearly observable positive value of 0.85 (a

stronger positive tail) at the highest shear rate presented. In this case the most-probable velocity

is quite diﬀerent from the average velocity, raising a fundamental question about the deﬁnition of

the actual ﬂuid velocity in terms of the observed particle velocity distribution. Figure 2.9 shows

the variation of the mean velocities as a function of shear rate, the error bars depict the standard

deviation about the mean. The velocities fall on a straight line through the origin, and there are no

discernible diﬀerences between the hydrophilic and hydrophobic surfaces and, more interestingly,

between the 200- and 300-nm diameter particles.

The reason for the observed increase in the distribution width and skewness can be explained

in terms of the observation range from which particle motions are recorded. At each shear plane,

the true velocity distribution for tracer particles has a Gaussian shape with a mean equal to the

ﬂow velocity at that plane, and standard deviation determined by the temperature and particle

size. However, any micro-PTV or PIV system, including the current TIRV integrates through the

observation range and thus samples particle motion from a range of shear planes over which the

mean velocity changes. Thus, for a ﬁxed observation range, the range of mean velocities sampled

increases as the shear rate increases, leading to the observed broadening of the velocity distribution

for the streamwise velocity. A similar argument can be used to explain the increasing skewness

at higher shear rates. Here, we note that, due to the presence of the wall, a particle is more

likely to move upwards (and thus experience a higher local velocity) than to move downwards (and

experience a lower local velocity). Thus, higher velocity ﬂuctuations are more probable than lower

ones in the vicinity near the wall (a similar argument is used to explain positive skewness in the

streamwise velocity distribution in a turbulent wall-bounded ﬂow).

The lack of any diﬀerences between the mean velocities obtained for 200-nm and 300-nm par-

ticles is more troubling. One would expect that the 300-nm particles would sample shear planes

at higher local velocities than those sampled by 200-nm particles, and thus the average velocities

17

0 500 1000 1500 2000 2500

0

100

200

300

400

Shear rate (1/sec)

A

p

p

a

r

e

n

t

v

e

l

o

c

i

t

y

(

μ

m

/

s

e

c

)

Figure 2.9: Apparent particle velocity vs. shear rate (♦, 300-nm particle, hydrophilic surface; ,

300-nm particle, hydrophilic surface; , 200-nm particle, hydrophilic surface; ◦, 200-nm particle,

hydrophilic surface).

should be larger for the larger tracer particles. The fact that this is not observed remains a some-

what puzzling result and one that needs to be resolved in future measurements. However, there are

several factors that are not yet well understood that could contribute to this counter-intuitive ob-

servation, including uncertainty in the measurement of the illumination observation range, particle

motions in addition to pure translation (such as rolling motion), and other forces on the particles

(e.g. colloidal).

The drift velocities measured can result from two eﬀects: (i) the ﬁnite thickness of the observa-

tion range and (ii) the possible existence of a slip velocity at the surface. We can assess the relative

contributions of these eﬀects using a very simple theoretical model. If we assume a constant shear

very near the surface, we can write the local velocity proﬁle as:

u(y) = u

s

+ ˙ γy, (2.7)

where u

s

is the slip velocity. If we use a Navier representation for the slip velocity, u

s

= l

∗

˙ γ, (where

l

∗

is the slip length) and compute the average velocity in the mean depth of the observation range,

δ, we ﬁnd that the average, or ”apparent slip” velocity is

¯ u = (l

∗

+δ) ˙ γ, (2.8)

The slope of the data in Fig. 2.9 is approximately 100-nm, representing this combination of

both the penetration depth and the slip length. Given that the observation range is estimated to be

approximately 100 - 150 nm, this suggests that the slip length, if present, is likely no more than 10

nm, consistent with the results of Choi et al. [25] for these low shear rates. At the present, our lack

of quantitative knowledge about the evanescent wave penetration depth (which probably varied

from experiment to experiment) and the observation range makes a more precise estimate for the

slip length impossible at this time. However, with the appropriate characterization and consistent

control of the observation range, this measurement will be possible and such experiments are

currently underway. Finally, we note that a slip length of order 1000 nm (as proposed by Tretheway

18

and Meinhart [30], and Zhu and Granick [64]) is completely unsupported by these data, as it would

predict apparent slip velocities at least an order of magnitude larger than observed, and would be

independent of any reasonable estimate for the observation range.

2.3.3 Comparisons with Numerical Simulations

The experimental results were compared with a numerical simulation of near-wall Brownian motion

in shear ﬂow. The motivation for this was to generate an intuitive model with which to help

understand the experimental results. This simple two-dimensional numerical model was developed

to simulate the Brownian motion of particles with radius, r, in a no-slip steady-state Couette ﬂow

between parallel inﬁnite plates separated by a distance h, the experimental channel depth. At

the beginning of the simulation, 10,000 particles were uniformly distributed between r and δ, the

assumed upper bound of the observation range. At each time step, each particle was moved by

a linear combination of the mean shear ﬂow (evaluated at the particle’s geometric center) and

Brownian motion (sampled from a normal distribution with a zero mean and a standard deviation

of

√

2D∆t). Other eﬀects such as particle rotation, etc were not considered at this time.

The Brownian motion was modiﬁed to account for the hindered diﬀusion both parallel and

perpendicular to the wall [36, 37, 38]. For the Brownian motion normal to the wall [36], the

modiﬁed diﬀusion constant, D

⊥

, is such that

D

⊥

D

0

=

_

4

3

sinh α

∞

n=1

n(n + 1)

(2n −1) (2n + 3)

_

2 sinh (2n + 1) α + (2n + 1) sinh 2α

4 sinh

2

_

n +

1

2

_

α −(2n + 1)

2

sinh

2

α

−1

__

−1

,

(2.9)

where D

0

is the Stokes-Einstein diﬀusion coeﬃcient, α = cosh

−1

(z/r) and z is the distance between

the geometrical center of a particle and the wall. For the Brownian motion parallel to the wall, the

modiﬁed diﬀusion constant, D

, is such that [37]

D

D

0

=1 −

9

16

_

h

r

_

−1

+

1

8

_

h

r

_

−3

−

45

256

_

h

r

_

−4

−

1

16

_

h

r

_

−5

+O

_

h

r

_

−6

,

(2.10)

by the method of reﬂection [37, 38] for (z −r)/r > 1, and

D

D

0

= −

2

_

ln

_

h−r

r

_

−0.9543

¸

_

ln

_

h−r

r

_¸

2

−4.325 ln

_

h−r

r

_

+ 1.591

, (2.11)

which is the asymptotic solution [37, 38] for (z −r)/r < 1.

After 1000 time steps, particles that remained within the observation range were counted and

their displacements from their initial positions were calculated to obtain a particle displacement

distribution, similar to that obtained in the physical experiments. To emulate the experiment,

plate separation distance, particle radii, ﬂow shear rate and the total time (1000 time steps) were

chosen to be equal to measurement conditions, and the assumed observation range was chosen to

be 100 - 175 nm from the wall.

19

200 0 200 400 600 800

0

0.005

0.01

0.015

0.02

Velocity(μm/sec)

P

D

F

234 (1/sec)

1172 (1/sec)

2344 (1/sec)

Figure 2.10: Streamwise velocity distribution of 200-nm particles determined from Monte Carlo

simulation at observation depth = 175 nm.

Problems can arise when the simulated particle is predicted to pass through the solid surface

during the ﬁnite time step. In the present simulation two diﬀerent wall boundary conditions were

tested to deal with this situation. The ﬁrst condition applied a specular reﬂection, in which particle

was simply reﬂected oﬀ the wall and back into the ﬂow. The second condition emulated near-wall

lubrication condition and simply allowed the particle to remain at the wall until Brownian motion

perpendicular to the wall transported it back into the bulk ﬂow, one or more time steps later. Only

a few particles needed to be treated with these heuristic boundary conditions, and it was found

that the two models gave almost indistinguishable results, with less than 1% statistical diﬀerence

in the mean and standard deviation of the resultant particle distributions. Figure 2.10 shows

the streamwise velocity distributions of 200-nm particles at various shear rates, while Fig. 2.11

shows the variation of the mean velocities and their standard deviations, denoted as error bars, as

a function of shear rate. The rather simplistic nature of the simulation is such that one should

not make direct, quantitative, comparisons with the experimental results (Fig. 2.8 and 2.9). In

addition, the choice of observation range for the computation has not yet been optimized to match

the simulation results with those of the experiments. Nevertheless, the similarities between the two

ﬁgures are striking, showing similar increases in the mean, standard deviation and (less obvious,

but present) skewness of the distributions as the shear rate increases.

Unlike the experimental results in Fig. 2.9 which did not show any diﬀerence in measuring

velocity using diﬀerent particle size, there is a clear diﬀerence in the estimated velocity using

diﬀerent particle size in Fig. 2.11. As discussed earlier this diﬀerence due to particle size is to

be expected for a ﬁxed observation range, and this result adds weight to our suspicion that the

observation range in the experiments were not consistent, and that future experiments should pay

more attention to this important issue.

20

0 500 1000 1500 2000 2500

0

100

200

300

400

500

Shear rate (sec

1

)

A

p

p

a

r

e

n

t

v

e

l

o

c

i

t

y

(

μ

m

/

s

e

c

)

Figure 2.11: Streamwise apparent velocity predicted by simulation (, 200-nm particles; ◦, 300-nm

particles) at the observation depth of 175 nm.

2.4 CONCLUDING REMARKS

We have demonstrated that Total Internal Reﬂection Velocimetry (TIRV) can be a very powerful

technique for the study of near-wall ﬂows in microﬂuidic systems. TIRV images have very low

background noise that allows accurate PIV and PTV measurements of ﬂow velocities within a few

hundred nanometers of the surface. By using sub-micron seed particles, we have demonstrated

the ability to measure both velocity distributions and mean velocities in the plane parallel to the

surface.

The determination of velocities in the streamwise and spanwise directions is extremely accurate,

and comparable to ”standard” microPIV techniques, and is limited by the same constraints - the

accuracy of particle centroid location, diﬀraction-limited imaging of sub-micron particles, etc [70].

However, the technique also promises the ability to use intensity information to obtain wall-normal

displacements as well as precise estimates for the slip velocity at the surface. The present imple-

mentation did not (unfortunately) control with suﬃcient accuracy or consistency the characteristics

of the evanescent wave penetration depth which is very dependent on the incident beam angle. For

this reason, we were not able to measure vertical particle motion and our current resolution of the

slip length measurement is limited such that we can only state that a slip length, if present, is of

order 10 nm or less. However, the estimate for the slip length is limited only by the accuracy with

which we can measure the observation range and so we expect to be able to make measurements

with uncertainties less than 5 nm in the near future.

The accuracy of the TIRV system can still be improved by several means that are subject to

future investigation. First, by using a shorter illumination wavelength, the penetration depth of

evanescent ﬁeld can be decreased. Secondly, smaller seed particles can move closer to the channel

surface than larger particles, although they also suﬀer from higher Brownian diﬀusion and so the

particle drop-out will increase. Both changes will allow direct measurements of ﬂow velocities that

are closer to the channel surface, where slip might contribute more signiﬁcantly to the local ﬂow

velocity.

21

Finally, and most importantly, the technique does raise fundamental questions regarding the

use of ”passive” tracer particles to estimate the velocity ﬁeld in microﬂuidic systems. Our results

reveal several features of particle motion in the near vicinity of the surface, including non-Gaussian

Brownian motion (due to the ﬁnite thickness of the observation range) and hindered diﬀusion due

to near-wall lubrication eﬀects. There are also eﬀects other than the translational hydrodynamic

drag that can contribute to the particle motion such that the velocity measurements might be

compromised. One is the possibility of particle rotation; a second is the possibility of particle-

wall colloidal interactions and the relative roles of gravity, thermal noise and electrostatic eﬀects

(both the bead and the surface have surface charges). This is an area that has been studied by

a number of researchers, including Flicker et al. [51], Crocker and Grier [75] and Behrens and

Grier [76] who have identiﬁed colloidal forces that are highly dependant on bead diameter, surface

charge, ionic strength (and for pure water such as used in these experiments, the rate at which

ions leak from the glass into solution). A full treatment of these issues is beyond the scope of the

current paper, and indeed, the experimental techniques described here to can be used in further

studies of such phenomena. Perhaps the most important consequence of this is that techniques that

treat ensembles of particles (such as PIV which looks at the collective motion of particles in an

interrogation region, and often averages cross-correlations before peak detection) might be suspect

close to walls due to particle interference eﬀects which cannot be neglected and where the particle

motion is not represented by Gaussian statistics (and hence the average particle velocity is diﬀerent

from the most probably particle velocity). For this reason, tracking each particle independently

and then computing statistics from the individual particle motions might yield a more accurate

view of the near-wall velocity ﬁeld.

Chapter 3

Paper 2: Direct measurement of slip

velocities using three-dimensional

total internal reﬂection velocimetry

The existence and magnitude of slip velocities between deionized water and a smooth glass surface

is studied experimentally. Sub-micron ﬂuorescent particles are suspended in water and imaged

using Total Internal Reﬂection Velocimetry (TIRV). For water ﬂowing over a hydrophilic surface,

the measurements are in agreement with previous experiments and indicate that slip, if present, is

minimal at low shear rates, but increases slightly as the shear rate increases. Surface hydrophobicity

is observed to induce a small slip velocity, with the slip length reaching a maximum of 96 nm at a

shear rate of 1800 s

−1

. Issues associated with the experimental technique and the interpretation of

results are also discussed.

3.1 INTRODUCTION

The century-old assumption of the no-slip boundary condition between a liquid and a solid has been

challenged by recent experimental results and molecular dynamic simulations and has been the

subject of many recent investigations exploring ﬂows over both wetting and non-wetting surfaces.

Although there is considerable disagreement regarding the existence of slip over a hydrophilic

surface, it is generally believed that surface hydrophobicity aids slip, while the exact mechanism

is not yet understood (for a review of this topic, see [7]). Experimental studies have reported

a wide range of slip lengths, ranging from micrometers [20, 30, 32, 64], hundreds of nanometers

[29, 33], to tens of nanometers or smaller (including no-slip) [25, 26, 27, 28, 31]. Molecular dynamics

simulations, on the other hand, suggest small slip lengths, mostly less than 100 nm [22, 23, 24, 77,

78, 79].

The experiments have been conducted under various direct and indirect measurement techniques

with varying accuracy and uncertainty. In indirect measurements, slip velocity is inferred from

other ﬂow quantities, such as the relationship between ﬂow rate and pressure drop [25] or the

measurement of the forces required to move a pair of crossed cylindrical surfaces separated by a

thin ﬁlm of the test ﬂuid [26, 27, 28, 64]. In contrast, alternative techniques such as micro-particle

image velocimetry (PIV) have resulted in direct measurements of near-surface ﬂuid velocity using

tracer particles [30, 31].

Although the direct measurements have a strong appeal, there are two major drawbacks inher-

22

23

ent to conventional micro-PIV. The ﬁrst is that the velocity is determined from the motion of a

collection of particles in an interrogation area (IA) and, in order to obtain a reasonable estimate of

the velocity, the IA must be measuring several hundred nanometers in size [30]. Hence the determi-

nation of phenomena which might measure a few nanometers is very diﬃcult to resolve. A second

problem is that the size of measurement volume along the optical axis for ﬂood-illuminated micro-

PIV techniques is deﬁned by the focal depth of the optical system, which is typically of the order

of 0.5 to 1 micron [30, 31]. Although Joseph & Tabeling [31] reported a slip length measurement

with 100-nm resolution, micro-PIV would still be insuﬃcient to provide an aﬃrmative conclusion

if the true slip length is below 100 nm.

One attractive approach that solves both of these problems is the use of Total Internal Reﬂection

Velocimetry (TIRV) [80] which uses total internal reﬂection of an incident laser pulse to generate a

highly localized illumination of the surface ﬂow, and relies on tracking the motion of single tracer

particles rather than the collective particle motion that is used in PIV. Total internal reﬂection

ﬂuorescence microscopy (TIRFM) has long been used by biologists to study near-surface dynamics

[65, 66, 67]. Zettner & Yoda [56] combined micro-PIV and TIRFM to study near-surface Couette

ﬂow while Pit et al. [29] measured slip velocity of hexadecane over a sapphire substrate using

TIRFM and ﬂuorescence recovery after photobleaching. We ﬁrst reported on the TIRV technique

in the context of slip velocities for near-wall microﬂows [80], but were unable to make a conclusive

determination of the size or character of any slip lengths due to diﬃculties in the determination

the location of tracer particles within the narrow evanescent illumination region.

The present manuscript reports on experiments in which the TIRV technique has been sub-

stantially improved to the point that quantitative statements can be made regarding the nature of

slip velocities over hydrophilic and hydrophobic surfaces. By measuring the intensity of tracer par-

ticles’ ﬂuorescence, and in conjunction with a statistical model for the optical and hydrodynamic

behaviour of small particles near a surface, we are able to track their motion within a narrow region

above the solid surface and to compare that motion to the motion predicted for diﬀerent levels of

boundary slip.

3.2 THEORETICAL CONSIDERATIONS

3.2.1 Total Internal Reﬂection Microscopy

The evanescent ﬁeld and its application to ﬂuorescence microscopy has been thoroughly documented

in literature [e.g. 40, 44, 47, 56, 63, 80]. In summary, an evanescent ﬁeld can be created near a

solid-liquid interface where total internal reﬂection occurs, as illustrated in ﬁgure 4.1. The ﬁeld

intensity, I, decays exponentially with distance, z, away from the two-medium interface by

I(z) = I

0

e

−z/p

, (3.1)

where I

0

is the intensity at the interface and p is known as the evanescent wave penetration depth.

The penetration depth, which characterizes the length scale of the evanescent ﬁeld, can be calculated

from

p =

λ

0

4π

_

n

2

1

sin

2

θ −n

2

2

_

−

1

2

, (3.2)

where λ

0

is the wavelength of the incident light, θ is the beam incident angle and n

1

and n

2

are

the indices of refraction of the solid and liquid, respectively.

24

Figure 3.1: Objective-based total internal reﬂection ﬂuorescence microscopy.

3.2.2 Emission Intensity of Fluorescent Particles

For spherical tracer particles with a uniform volumetric ﬂuorophore distribution in an evanescent

ﬁeld, Kihm et al. [44] calculated the particles’ emission intensities as an exponential function

of their distances to a substrate surface. Through experience we have found, however, that the

intensity of ﬂuorescence emission from a large number of nominally identical particles can vary due

to a variety of factors, including statistical variations in illumination intensity, quantum eﬃciency of

the imaging system and, most importantly, a distribution in the physical size of the particles. If we

parameterize all of these variations by an “eﬀective emission radius”, r, we can model the particle’s

probability density function (PDF) of its eﬀective emission radius with a Gaussian distribution

P(r) = P

0

exp

_

−

_

r

a

−1

_

2

σ

2

r

_

, (3.3)

where a is the mean eﬀective emission radius of the batch, σ

r

is the characteristic variation (standard

deviation) and P

0

is a normalization constant. Based on the calculation of Kihm et al. [44] and

the assumption that emission intensity of a ﬂuorescent particle is proportional to the number of

ﬂuorophores within its volume, the emission intensity, I

e

, of a particle in an evanescent ﬁeld is

I

e

(r, h) =

_

r

a

_

3

_

I

e

0

e

−(h−a)/d

_

, (3.4)

where h is the distance from the particle’s centre to the substrate surface at which total internal

reﬂection occurs, I

e

0

is the emitted intensity of a single particle with r = a located at h = a (ie.

touching the substrate surface), and d is an intensity decay length that need not be the same

as the evanescent penetration depth. The intensity decay length can be obtained experimentally

by statistically measuring intensities of particles as a function of particles’ distances away from

the substrate. Combining (3.3) and (3.4), one gets the joint PDF of the emitted intensity and a

particle’s distance to the substrate as

P(I

e

, h) = αexp

_

¸

¸

¸

_

¸

¸

¸

_

−

_

3

_

_

I

e

I

e

0

_

e

(h−a)/d

−1

_

2

σ

2

r

_

¸

¸

¸

_

¸

¸

¸

_

. (3.5)

25

0 0.5 1 1.5 2 2.5

0

0.5

1

1.5

Normalized Intensity

P

D

F

σ

r

= 0.05

σ

r

= 0.1

σ

r

= 0.15

σ

r

= 0.2

Figure 3.2: The emission intensity distribution of particles in a uniform concentration ﬁeld. The

normalized intensity in the horizontal axis is deﬁned as I

e

/I

e

0

, and the calculation is performed

with a normalized observation range of 0 < h/a < 3 and a normalized intensity decay length of

d/a = 1.8.

When an ensemble of tracer particles are imaged, they would certainly be located at a range of

distances from the substrate surface. The lower limit of this imaging range is h = a, representing a

particle touching the substrate surface. The upper limit of the imaging range is determined by the

sensitivity of the recording medium, such as an intensiﬁed CCD camera used in this study. For a

given imaging range of h

1

< h < h

2

, the PDF of a tracer particle’s intensity is given by

P(I

e

, h

1

< h < h

2

) =

_

h

2

h

1

P(I

e

, h)c(h) dh, (3.6)

where c(h) is the concentration proﬁle of particles in the ﬂuid. A sample plot of this distribution

(3.6) is shown in ﬁgure 3.2 for a range of values of σ

r

. For a low variation in eﬀective emission

radius (σ

r

small), we see that the particles in the deﬁned imaging range are sharply deﬁned in

intensity, with the brightest particles located at the surface (I

e

/I

e

0

= 1) and the faintest particles

at the outer edge of the evanescent ﬁeld (I

e

/I

e

0

= 0.2). However, as the variation in particle radius

increases, the transitions become more blurred, and some larger particles close the wall contribute

to the long tail at high observed intensities, while small particles close to the edge of the imaging

range are represented by the smooth transition close to I

e

/I

e

0

= 0.

When performing image analysis, however, one need not analyse all imaged particles. Instead,

using particle intensity as a guide, one can choose to identify and analyse only the particles within

a certain desirable intensity range, ignoring particles that appear too bright or too dim. Equation

(3.5) could also describe the particle position distribution within a normalized intensity range of

α < I

e

/I

e

0

< β by

P (h, α < I

e

/I

e

0

< β) = c(h)

_

β

α

P(I

e

, h) d

_

I

e

I

e

0

_

. (3.7)

26

100 150 200 250 300 350

0

2

4

6

8

x 10

−3

Particle Center Distance to Wall (nm)

P

D

F

Figure 3.3: The predicted position distribution of particles with 0.5 < I

e

/I

e

0

< 1 in a uniform

concentration ﬁeld. In this prediction, a = 100 nm, d = 181 nm and σ

r

= 0.18.

An example of this position distribution (3.7) is shown in ﬁgure 3.3 for a normalized intensity

range of 0.5 < I

e

/I

e

0

< 1. The most obvious feature of ﬁgure 3.3 is that the distribution is non-

uniform with the majority of particles contributing to this range of intensities coming from close

to the substrate surface (< 250 nm). In addition, one can observe that the distribution has a long

positive tail that gradually decays to zero at far away into the ﬂuid bulk. Because of the large

particle eﬀective radius variation in this example, a large particle far away (for example, > 300

nm) can exhibit in the same the same ﬂuorescence intensity as that of smaller particles close to

the substrate surface. These observations reinforce the fact that a particle’s intensity cannot be

monotonically related to its distance to the solid surface, and attention should be given to any

intensity-based quantitative analysis by recognizing the non-uniform position distribution and the

contribution of particles far away from wall.

3.2.3 Near-Surface Shear Flow

Although we are interested in determining the velocity of a pure ﬂuid near a solid surface, we

actually measure the velocity of small spheres near the surface, and it is critical to recognize the

diﬀerences between these two quantities. It is well known that shear and near-surface hydrodynamic

eﬀects can cause a tracer particle to rotate and translate at a velocity lower than the local velocity

of the ﬂuid in the same shear plane [12, 38]. Goldman et al. [38] proposed that a particle’s

translational velocity, U, in a shear ﬂow with local shear rate, S, is given by

U

hS

· 1 −

5

16

_

h

r

_

−3

, (3.8)

valid for large h/r, and

U

hS

·

0.7431

0.6376 −0.2 ln

_

h

r

−1

_, (3.9)

27

1 1.5 2 2.5 3 3.5 4

0.4

0.5

0.6

0.7

0.8

0.9

1

h

2

/r

¯

U

¯

V

h

1

/r = 1

h

1

/r = 1.5

Figure 3.4: The ratio of statistical apparent velocity of particles and mean ﬂuid velocity under no

slip in an imaging range of h

1

< h < h

2

, which is non-dimensionalized by particle radius.

¯

V is

computed with linear ﬂuid velocity proﬁle, which is a good approximation near a surface. In the

computation of

¯

U, c(h) is assumed to be uniform.

valid for small h/r. Although there exists no analytical approximation for intermediate values of

h/r, Pierres et al. [60] proposed a cubic approximation to numerical values presented by Goldman

et al. [38]:

U

hS

·

_

r

h

_

exp

_

0.68902 + 0.54756

_

ln

_

h

r

−1

__

+ 0.072332

_

ln

_

h

r

−1

__

2

+0.0037644

_

ln

_

h

r

−1

__

3

_

.

(3.10)

The apparent velocity,

¯

U, of a large ensemble particles chosen from a normalized intensity range of

α < I

e

/I

e

0

< β and located in an imaging range of h

1

< h < h

2

is given by the average of the local

velocity integrated over the imaging range:

¯

U =

1

h

2

−h

1

_

h

2

h

1

U (h, a, S (h)) P(h, α < I

e

/I

e

0

< β) dh. (3.11)

This average apparent velocity,

¯

U, can be compared to the mean velocity, of the pure ﬂuid,

¯

V ,

calculated for the same imaging range. The ratio of the two is shown in ﬁgure 3.4, from which

we see that the average apparent velocity of particles is, not surprisingly, signiﬁcantly lower than

that of pure ﬂuid velocity when the imaging range is very close to the substrate surface. This

diﬀerence must be incorporated into the data analysis, and failure to recognize this eﬀect can lead

to misinterpretation of the measured data and underestimation of slip lengths.

It should be noted that (3.11) is based on a no-slip condition at the ﬂuid/solid interface. If

there exist a slip velocity, U

slip

, at the solid boundary, the apparent velocity of the same ensemble

28

of particles would be

¯

U

app

= U

slip

+

¯

U = δS

w

+

¯

U, (3.12)

where the slip velocity is characterized as the product of the slip length, δ, and the wall shear rate,

S

w

.

3.3 EXPERIMENTAL PROCEDURES

3.3.1 Materials and Setup

A schematic of the image acquisition system is shown in ﬁgure 3.5. Fluorescent particles were

illuminated with an objective-based TIRFM method, as detailed in [80]. A pair of 532-nm, 5-

nsec laser pulses (Quantel Twins Q-Switched Double Pulse Nd:YAG Laser) were directed through

a Nikon PL Apo NA 1.45 100X TIRF oil immersion objective at an angle that created total

internal reﬂection at a glass-water interface, thus illuminating the near-surface region of water with

an evanescent ﬁeld (ﬁgure 4.1). Fluorescent images of near-surface particles were projected onto

a Q-Imaging Intensiﬁed Retiga CCD camera (ICCD), capable of recording 1360-pixels-by-1036-

pixels 12-bit images. Under 100X magniﬁcation, each image pixel corresponds to 64.3 nm in the

ﬂow channel and the diﬀraction-limited spot size is 19.7 µm (calculated based on [70]). A TTL

pulse generator (Berkeley Nucleonics Model 555) was used to synchronize laser pulses and image

acquisitions. The energy of each illuminating laser pulse was recorded simultaneously with each

image acquisition and this was used to adjust the resultant images and thus account for pulse-to-

pulse variations in illumination intensity.

Test channels were fabricated using a polydimethylsiloxane (PDMS) (Dow Corning Sylgard 184)

molding technique [69] and bonded onto polished glass wafers. The dimensions of the test channels

were 50 ± 1 µm deep, 250 ± 1 µm wide and 15 mm long. To create hydrophilic microchannels,

the pre-bonding PDMS surface was exposed to an oxygen plasma and immediately immersed in

deionized-water after bonding to a glass wafer. Hydrophobic channels, on the other hand, were

fabricated by bonding untreated PDMS channels onto octadecyltrichorosilane(OTS)-coated glass

wafers. Detailed coating procedures can be found in [80]. It has been reported that water has a

contact angle of 120 degrees with a similarly prepared OTS-coating [30, 81]. The roughness of the

test surface was measured using an atomic force microscope prior to bonding. The hydrophilic and

hydrophobic surfaces had an RMS surface roughness of 0.47 nm and 0.35 nm respectively.

Monodisperse Fluorescent Polystyrene Microspheres (Duke Scientiﬁc) with diameters of 200 nm

(± 5%) suspended in puriﬁed water (Fluka) at 0.04% volume fraction were used as tracer particles

in this experiment. These microspheres have a peak absorption wavelength of 542 nm and emit a

red light at 612 nm. There are three reasons that 200-nm diameter particles were selected as probes

in this experiment. First, smaller size ﬂuorescent particles have much larger size variation, making

relation of particle center distance from the solid wall and their ﬂuorescent intensities less reliable.

Secondly, smaller particles do not contain enough ﬂuorophores to provide signiﬁcant signals with

a 5-nsec laser illumination. Lastly, 200-nm particles do not diﬀuse too far during the inter-frame

time, with diﬀusion out of imaging range being our major concern.

A Harvard Apparatus 22 syringe pump was used to maintain particle solution ﬂow rates, ranging

from 1 to 10 µL/min (±0.35%). To maintain steady pumping motions of the Harvard Apparatus

stepper motor, we purposely introduced a large volume of air between the piston and the ﬂuid in

the syringe. This volume of air acted as a pressure shock absorber to damp out the oscillatory

forcing of the syringe pump screw. In addition, a long tubing (> 1 m long) was used to connect

29

ICCD

Nd-YAG laser

532 nm

Syringe pump

100X, NA = 1.45

Objective lens

Dichroic mirror and

Barrier filter

PDMS channel

Convex lens

Pulse generator

Computer

1360 x 1036

x 12 bit

532 nm, 5 nsec pulse

2 - 5 ms separation

Power

Attenuator

Half-wave

plate NI_DAQ

Mirror

Convex Lens

10 micron pinhole

Convex Lens

Polarizing

Beamsplitter

Pulse Energy

Meter

Figure 3.5: Image acquisition system.

the syringe and the channel inlet. Particle ﬂow motion was observed to be very steady under this

setup.

1200 images were captured at each ﬂow rate, as well as in quiescent ﬂuid. Once all necessary

images of particle motion were captured, the test channel was ﬁlled with rhodamine-B solution.

Images of the rhodamine-B solution were subsequently captured under the same evanescent illumi-

nation, and averaged to obtain an image characterizing the spatial distribution of the illuminating

laser beam.

It has been suggested that nanobubbles and a gas bubble layer on hydrophobic surfaces could

be alternative sources of apparent slip [7, 34, 82]. Prior to each experiment, the ﬂuid was degassed

by placing the solution in vacuum for at least 30 minutes. This procedure has been reported to

signiﬁcantly eliminate nanobubble formation [83].

It is intuitive to assume that one can infer the location of a particle in the evanescent illumination

ﬁeld based on the ﬂuorescence intensity. Kihm et al. [44] used a ratiometric ﬂuorescence intensity

to track particle motions three-dimensionally. Although this is theoretically feasible, in practice,

successful use of this technique requires precise knowledge of the illumination beam incident angle

and a solution of Maxwell’s equation for an evanescent ﬁeld in a three media system (glass, water

and polystyrene), which can be diﬃcult to express explicitly. Thus, an experimental method was

devised to obtain a ratiometric relation between particle emission intensity and its distance to the

glass surface. We attached individual ﬂuorescent particles to ﬁne tips of glass micropipettes, which

were translated perpendicularly to the glass substrate in the evanescent ﬁeld with a 0.4-nm precision

stage (MadCity Nano-OP25). At each distance to the surface, 30 images of the attached particles

were captured. The pixel values of the imaged particles were then averaged, and subsequently ﬁtted

to a two-dimensional Gaussian function to ﬁnd their centre intensities. The process was repeated

30

0 50 100 150 200

0

0.2

0.4

0.6

0.8

1

h−r, (nm)

N

o

r

m

a

l

i

z

e

d

C

e

n

t

e

r

I

n

t

e

n

s

i

t

y

Figure 3.6: Fluorescent particle intensity as a function of its distance to the glass surface. The

particles used here are 200 nm in diameter. The solid line is a least-square exponential ﬁt to the

data whose decay length, λ, is 181 nm.

several times with diﬀerent particles. The particle intensities are shown in ﬁgure 3.6, along with a

exponential ﬁt to the measured data:

I

peak

= Ae

−λ(h−r)

+B, (3.13)

where A, B and λ are constants determined by a least-squares ﬁt. The ﬁtted curve predicts an

intensity decay depth of 181 nm, very close to the evanescent penetration depth that we would

predict based on the imaging lens, wavelength and refractive indices of the system.

3.3.2 Velocimetry Analysis

The analysis of particle image pairs was performed using a custom particle-tracking program written

in a MATLAB environment. Prior to velocimetry analysis, images of particles stuck on the glass

substrate had to be removed from each image pair to prevent undesirable detection by the Particle

Tracking Velocimetry (PTV) algorithm. Although the presence of these stuck particles could distort

the velocity ﬁeld, they generally had a very low density and were usually placed at the edge of an

image and far away from where the velocimetry measurements were performed. For each image, the

signals due to stuck particles and background noise were removed by subtracting a reference image

formed from the rolling average of 10 previous and 10 subsequent image pairs. To account for laser

pulse energy ﬂuctuation, every image was scaled by the measured laser illumination energy.

Velocimetry analysis started with ﬁnding the positions and peak intensities of all particles

via threshold-identiﬁcation and Gaussian ﬁtting of the intensities of the pixels surrounding the

peak. Subsequently each particle’s displacement was obtained with a limited-range nearest-neighbor

matching, and the displacement was decomposed into streamwise and cross-stream components

(for details of the tracking algorithm, see [80]). The particle seeding density was low enough such

31

0 0.5 1 1.5 2

0

0.5

1

1.5

2

P

D

F

Intensity Ratio (I

e

/I

e

0

)

Figure 3.7: Observed ﬂuorescent particle intensity distribution and its probability density function

(PDF). The solid line represents the theoretical prediction (3.6) for an imaging range of 100 to 400

nm and a 15% intensity statistical variation with a uniform concentration distribution of particles.

that this tracking was unambiguous. Intensities of the “trackable” particles were converted to a

normalized intensity ratio obtained by dividing the raw intensity counts by the average of all the

stuck particles’ initial intensity counts. Finally, particles within a desired normalized intensity range

were selected for each ﬂow rate and their mean streamwise velocity was deﬁned as the apparent

velocity of the ensemble. For the hindered diﬀusion analysis, the same analysis steps were followed

except that diﬀusion coeﬃcients of particles in quiescent ﬂuid were obtained from the variance of

displacements instead of velocities.

3.4 RESULTS AND DISCUSSION

3.4.1 Validation of Intensity Calibration Curve

Figure 3.7 shows the distribution of particle intensities recorded during a typical data acquisition

(in this case, in quiescent ﬂuid). The accompanying solid line is the theoretical prediction (3.6),

assuming an imaging range of 100 - 400 nm, and an eﬀective emission radius variation of σ

r

= 0.15.

The good agreement between the observed and predicted intensity variation conﬁrms our calibration

results and the statistical theory of the observed particle intensities discussed earlier.

3.4.2 Hindered Diﬀusion

Near-surface tracer particles are known to exhibit anisotropic hindered diﬀusion due to hydrody-

namic eﬀects, and the hindered diﬀusion coeﬃcient in the direction parallel to the substrate surface

32

0 0.5 1 1.5 2

0

0.2

0.4

0.6

0.8

1

(h−a)/a

D

e

x

p

/

D

0

Data 1

Data 2

Method of Reflection

Figure 3.8: Ratio of hindered diﬀusion coeﬃcients (D

exp

) for Brownian motion parallel to a surface.

D

is [37]

D

D

0

= 1 −

9

16

_

h

r

_

−1

+

1

8

_

h

r

_

−3

−

45

256

_

h

r

_

−4

−

1

16

_

h

r

_

−5

+O

_

h

r

_

−6

, (3.14)

where D

0

is the Stokes-Einstein diﬀusivity of a spherical particle in the ﬂuid bulk. This “Method

of Reﬂection” approximation is generally valid for (h − r)/r > 1. For (h − r)/r < 1, Goldman et

al. [38] proposed an asymptotic solution,

D

D

0

= −

2

_

ln

_

h−r

r

_

−0.9543

¸

_

ln

_

h−r

r

_¸

2

−4.325 ln

_

h−r

r

_

+ 1.591

. (3.15)

The combination of our particle-tracking algorithm and the intensity calibration curve was

applied to analyse near-surface particle Brownian motion parallel to the glass substrate. The

results are compared to the Methods of Reﬂection calculation (3.14) and shown in ﬁgure 3.8. The

experimental data shows reasonably good agreement with the theory, including the fall in the

eﬀective diﬀusion coeﬃcient close to the surface. The results further improve our conﬁdence in the

overall experimental method and subsequent analysis.

3.4.3 Velocity Distributions of Particles

Figure 3.9 shows distributions of particle velocities at three diﬀerent shear rates. Note that the

streamwise velocity distributions widen as shear rate increases, and their asymmetric shapes show

an increasing skewness as the shear rate increases. The increasing distribution width and skewness

at high shear rates are both results of sampling particle displacements from an imaging range with

ﬁnite thickness [80]. Physically, at higher shear rates, the ﬁnite-thickness imaging range contains

particles that are translated by a wider range of local velocities, hence the increasing width of the

33

−200 0 200 400 600 800 1000

0

0.005

0.01

0.015

0.02

Particle Velocity (µm/sec)

P

D

F

S = 183 sec

−1

S = 732 sec

−1

S = 1465 sec

−1

Figure 3.9: Distribution of observed particle streamwise velocities under various shear rates. Data

include measurements of ﬂow over a hydrophobic surface.

apparent velocity distributions. In addition, because the particles are conﬁned by the solid wall,

they are more likely to move away from the wall and into a faster moving shear plane. Thus the

distribution exhibits a more pronounced positive skewness at the higher shear rates.

The eﬀect of shear with a ﬁnite-thickness imaging range can be characterized if the streamwise

particle velocity in ﬁgure 3.9, V , is scaled by

˜

V =

V −¸V )

¸V )

, (3.16)

where

˜

V is the scaled streamwise particle velocity and ¸V ) is the mean value of each velocity

distribution. The scaled velocity distributions are shown in ﬁgure 3.10. At each shear rate, the

relatively contributions of velocities from shear ﬂow and Brownian motion can be characterized

by the Peclet number, Pe. Here the Peclet number is deﬁned as the ratio of the shear-induced

displacement, L, to the diﬀusive displacement, s, during the interframe time period, ∆t,

Pe =

L

s

=

¸V ) ∆t

√

2D

0

∆t

. (3.17)

Because ¸V ) is shear-dependent only, the shear-induced eﬀects in all velocity distributions in

ﬁgure 3.10 are scaled to equal magnitudes. It can be observed that small Peclet numbers are

associated with greater distribution widths while the distributions collapse onto a single skewed

distribution at high Peclet numbers. The explanation is the following: at low Peclet numbers the

distributions widths scale inversely to shear, suggesting a diﬀusion dominance and thus the large

widths of the velocity distributions are due to Brownian motion. As the Peclet number increases, the

eﬀect of shear ﬂow on particle motion increases and when Pe > 3, particle motions are completely

shear-dominant, causing the distributions to overlap. It should be noted that the overlapping

34

−1.5 −1 −0.5 0 0.5 1 1.5

0

0.5

1

1.5

Scaled Particle Velocity

P

D

F

Pe = 1.20

Pe = 1.93

Pe = 3.28

Pe = 4.16

Pe = 4.43

Pe = 5.52

Figure 3.10: Distribution of observed particle streamwise velocities after scaling the velocities

distributions in ﬁgure 3.9. The velocities are scaled according to (3.17). Pe of 1.20, 3.28 and 4.43

correspond to the shear rates of 183, 732 and 1465 sec

−1

in ﬁgure 3.9, respectively.

distributions have the same distribution width, asymmetric shape and the same positive tail, which

are absent in small Peclet number cases. These observations conﬁrm the explanation that in ﬁgure

3.9, the increasing distribution width and skewness at high shear rates are both eﬀects of shear.

3.4.4 Measurements of Apparent Slip Velocities

For each ﬂow case, the intensity distribution of all “trackable” particles were compared to the

theoretical prediction (3.6) to identify the unknown parameters such as h

1

, h

2

and σ

r

through

optimization, as demonstrated in section 3.4.1 and ﬁgure 3.7. With these parameters known,

we calculated the theoretical apparent velocities of a particle ensemble, chosen from a normalized

intensity range, by using equation (3.12) and varying the slip length conditions. Subsequently, these

velocities were compared to the experimental apparent velocities (mean values of the streamwise

velocity distribution) of particles from the same normalized intensity range to extract experimental

slip velocities and slip lengths.

Figures 3.11 and 3.12 show the experimental and theoretical apparent velocities as a function

of wall shear rate over hydrophilic and hydrophobic surfaces, respectively. In both ﬁgures, the

solid lines represent the theoretical apparent velocities assuming zero slip (equation (3.11)). The

dashed and dotted lines are the expected apparent velocities if one were to assume a 50-nm and

a 100-nm slip length, respectively (calculated using (3.12)). In the case of the hydrophilic surface

(ﬁgure 3.11), the measured slip length ranges from 26 to 57 nm with a slightly increasing trend as

wall shear rate increases. The data obtained for ﬂow over the hydrophobic surface (ﬁgure 3.12),

on the other hand, suggests a larger slip length ranging from 37 to 96 nm, with a more observable

increasing trend of wall shear rate dependence at higher shear rates. A quantitative comparison of

the two cases shows a slip length attributed to surface hydrophobicity ranging from -7 nm at low

35

0 500 1000 1500 2000

0

100

200

300

400

500

600

700

Wall Shear Rate (1/sec)

A

p

p

a

r

e

n

t

V

e

l

o

c

i

t

y

(

µ

m

/

s

e

c

)

No Slip (Theoretical)

Slip length = 50 nm

Slip length = 100 nm

Exp. data

Figure 3.11: Experimental apparent velocity of particles in a shear ﬂow over a hydrophilic surface

(0.21 < I

e

/I

e

0

< 0.78), and its comparison to slopes of expected apparent velocities if there exists

a 0, 50 or 100-nm slip length. The error bar of each experimental data point represents a 95%

conﬁdence interval. In all cases the 95% conﬁdence intervals are within ±3% of the reported mean

velocity values.

shear rates to 54 nm at the highest tested shear rate, with an average value of 16 nm in between

(ﬁgure 3.13). The additional slip caused by surface hydrophobicity is in agreement with many

experimental results [25, 26, 28, 31], but is in sharp disagreement with others [30, 33, 64].

There are three possible sources of measurement uncertainty in ﬁgure 3.11 and 3.12: determina-

tion of (a) the wall shear rate, (b) the apparent velocities of particle ensembles and (c) the imaging

range. Because wall shear rates are calculated based on microchannel dimensions and ﬂow rates

which are controlled by the syringe pump, we estimate that the uncertainty in the wall shear rates

is less than 3%. If there is signiﬁcant slip at the wall, the shear rates could be slightly lowered than

the reported values. However, the largest observed slip length is less than 1% of the channel height,

and thus the slip eﬀect on wall shear rate calculation can be safely neglected. The determination of

apparent velocities of particle ensembles also has extremely low uncertainly because central limit

theorem constrains the statistical mean of a large sample (a few thousand trackings) to a very low

uncertainty (< ±3% of the reported velocity values for 95% conﬁdence intervals). In addition, with

subpixel resolution of the particle centre detection, our PTV algorithm is able to track particle

displacements with high accuracy (< 0.1 pixel, [84]). The largest source of uncertainty is the deter-

mination of the imaging range. The imaging range is determined statistically based on the particle

intensity decay length obtained from ﬁgure 3.6 where intensity measurements were performed in

increments of 20 nm, which could serve as the upper limit of imaging range uncertainty. However,

it should be noted that, with an uncertainty of 20 nm taken into consideration, the largest mea-

sured slip length still will not exceed 150 nm – much smaller than other experimental studies which

reported slip lengths greater than a few hundred nanometers.

One should note that the corrections due to shear-induced rotation (ﬁgures 3.11 and 3.12) do

36

0 500 1000 1500 2000

0

100

200

300

400

500

600

Wall Shear Rate (1/sec)

A

p

p

a

r

e

n

t

V

e

l

o

c

i

t

y

(

µ

m

/

s

e

c

)

No Slip (Theoretical)

Slip length = 50 nm

Slip length = 100 nm

Exp. data

Figure 3.12: Experimental apparent velocity of particles in a shear ﬂow over a hydrophobic surface

(0.5 < I

e

/I

e

0

< 1.0), and its comparison to slopes of expected apparent velocities if there exists

a 0, 50 or 100-nm slip length. The error bar of each experimental data point represents a 95%

conﬁdence interval. In all cases the 95% conﬁdence intervals are within ±3% of the reported mean

velocity values.

0 500 1000 1500 2000

−20

0

20

40

60

Wall Shear Rate (1/sec)

A

d

d

i

t

i

o

n

a

l

S

l

i

p

L

e

n

g

t

h

(

n

m

)

Figure 3.13: The additional slip length due to surface hydrophobicity.

37

not account for the possibility of slip between the ﬂuid and the tracer particle, and we are unaware

of any work that extends the theory of Goldman et al. [38] to include the eﬀect of surface slip.

Physically, surface slip is unlikely to be an issue, because the tracer particles have relatively rough

surfaces. Nevertheless, we can qualitatively estimate its eﬀect. Slip between the ﬂuid and the

tracer particle will modify the particle velocity in two ways. Firstly, the reduced shear force will

result in the particle velocity lagging the local ﬂuid velocity. Secondly, however, slip will reduce

the shear-induced rotation of the particle. Since these two mechanisms act in opposition to each

other, we believe that, as a ﬁrst approximation, we can ignore this eﬀect.

Granick et al. [34] and Lauga et al. [7] both pointed out that large surface roughness can

signiﬁcantly decrease slip. The slip length we measured with sub-nanometer surface roughness,

however, agrees well with the surface roughness dependency reported by Zhu & Granick [26]. It

should also be noted that Joseph & Tabeling [31], with ﬂow experiments conducted under similar

surface roughness, hydrophobic coating and shear rates, reported slip length very close to the

present results. It has also been suggested that electrokinetic eﬀects could signiﬁcantly aﬀect

velocimetry measurements of suspended particles close to a surface. Lauga [35] reported that a

streaming potential can induce electrophoretic motion of particles if particle surfaces are charged,

and applying this theory to the current conditions results in an “apparent” slip length of at most

18 nm.

Electrostatic interaction between tracer particles and surface could also aﬀect accuracy of ve-

locimetry measurements [7]. If the tracer particles and the substrate surface are similarly charged,

electrostatic repulsion can create a depletion layer near the substrate surface that eﬀectively shifts

the imaging range. Because the slip length calculations in ﬁgure 3.11 and 3.12 are based on the

assumption that particle concentration is uniform near surface, a depletion layer could be a source

of “apparent slip” if it is not recognized. Lumma et al. [33] suggested that the depletion layer

thickness can be as large as 0.9 µm for a pure water and glass combination. Such a thickness seems

unreasonably large as it is much bigger than the evanescent ﬁeld penetration depth and conse-

quently few ﬂuorescent particles would be observed. In contrast, Flicker et al. [51] experimentally

measured the depletion layer thickness to be in the order of 10 to 30 nm. For our experimental

setup, calculations suggest that, based on the overall particle seeding density, if the particles are

uniformly distributed in the ﬂuid one should be able to see around 19 particles in a 26 µm-by-26

µm image ﬁeld. This is in close agreement with our experimentally-derived images, and we can

conclude that the depletion layer thickness must be much smaller than our imaging range and

thus eﬀects due to a depletion layer thickness of this magnitude would not be detectable with our

current imaging technique. However, recognizing the possibility of such depletion layer’s existence,

we re-analysed the theoretical curves in ﬁgure 3.11 and 3.12 by assuming an imaging range farther

away from the substrate surface. We found such a shift would result in higher theoretical apparent

velocities of particle ensembles and therefore lower slip lengths for all shear rates, suggesting that

our reported slip lengths are most likely the upper bound of the true slip length value.

The electrostatic and electrokinetic interactions are an interesting pair as their signiﬁcance de-

creases with increasing ionic strength of the test ﬂuid. Perhaps a more accurate direct measurement

of the true surface slip can be obtained if aqueous solutions of moderately high ionic strengths were

used.

3.5 CONCLUDING REMARKS

The results presented here represent direct measurements of local velocities in the near wall region

of a ﬂuid-solid boundary. Despite the relative simplicity of the experiment, several subtle issues

38

need to be carefully addressed, including the spatial non-uniformity of the illumination region, the

eﬀects of the local shear on the dynamics of seeding particles, and the statistical variations in the

eﬀective visibility of the seeding particles. The current experiment conﬁrms previous measurements

in our own group [25] as well as some other recent measurements [26, 31] that there is minimal slip

over hydrophilic surfaces, and that hydrophobic surfaces do appear to introduce a discernable, but

small boundary slip.

Although the present technique does allow for measurement of particle motions very close to the

solid surface, it does suﬀer from some limitations and there is room for improvement. Most notably,

the tracking in the wall-normal direction is currently limited to an accuracy of approximately 10%

of the evanescent penetration depth (about 20 nm in the current case). If particles with a higher

degree of monodispersity can be reliably found, and if the imaging system noise can be reduced

(both of which are technical improvements on the immediate horizon), we believe that the technique

can be used to track particles with an order of magnitude improvement in accuracy. However, even

with the current levels of uncertainty, there is no possibility that the ﬂow exhibits a slip length

more than 150 nm (ﬁgure 3.12) over the range of shear rates tested.

While the debate of slip versus no-slip will likely continue in the foreseeable future, we believe

that a consensus is forming from more recent experiments that the slip eﬀect is not as extreme

as some studies might have suggested. As many authors have pointed out, measurement and

interpretation of slip data in the nanoscale can be very tricky because other physical phenomena,

such as electrokinetics and nanobubbles, might lead to observations of an “apparent slip” caused by

other complicating factors. All of these suggest that close attention must be to paid to documenting

the experimental conditions, and that this might well reveal the reasons behind the range of reported

apparent slip phenomena.

Chapter 4

Paper 3: Direct measurement of slip

length in electrolyte solutions

The emergence of microﬂuidics over the past decade has brought out increased research interests

in liquid boundary slip, which for centuries has been regarded as negligible. Advancements in

ﬂow measurement techniques have resulted in many recent experiments reporting aqueous slip

length with a wide range of values and various degrees of dependency on applied shear rate, surface

hydrophobicity and surface smoothness [20, 21, 25, 26, 28, 30, 31, 32, 33]. A total internal reﬂection

velocimetry (TIRV) technique was recently reported to be an eﬀective method in measuring liquid

velocities in the region of less than 300 nm from solid surfaces [80]. By conducting a three-

dimensional TIRV (3D-TIRV) experiment, Huang et al. reported that slip length can be obtained

within a 20-nm uncertainty [85]. They reported a small but non-negligible slip length for de-ionized

aqueous solutions in shear ﬂows over both hydrophilic and hydrophobic surfaces. However, some

questions remained as to whether electrostatic and/or electrokinetic forces acting on the tracer

particles could lead to false slip observation [7, 35]. In this letter, slip length measurement of ionic

aqueous solutions using TIRV is presented and compared to the previous results of Huang et al. as

an attempt to answer these open questions.

The TIRV technique uses total internal reﬂection of an incident laser beam to generate a highly

localized illumination of the near-boundary liquid phase, and relies on tracking motions of individual

tracer particles to determine ﬂuid velocity vectors in the planes parallel to a solid surface (as

demonstrated in ﬁgure 4.1). The exponentially decaying evanescent ﬁeld leads to determination

of tracer particles’ positions in the direction normal to the solid surface based on their ﬂuorescent

intensities. Subsequently slip velocities and slip length can be inferred from the measured apparent

velocity vectors by applying a statistical model for optical and hydrodynamic behaviors of small

particles near a solid/liquid interface. A detailed description of the 3D-TIRV theoretical work,

including a proof of concept and a discussion of its subtleties, was presented by Huang et al. [85].

A brief summary is presented in this letter to facilitate the readers’ understanding and resultant

discussion.

When a ﬂuorescent particle of radius a is illuminated by an evanescent ﬁeld of incident wave-

length λ

0

(a < λ

0

), its emission intensity, I

e

, exhibits the same exponentially decaying characteristic

as the evanescent ﬁeld energy does, namely,

I

e

(z) = I

e

0

e

−h/p

, (4.1)

where h is the distance between the particle center and the solid phase, I

e

0

is the emission intensity

of the particle when it is in contact with the solid phase (h = a), and p is the evanescent wave

39

40

Figure 4.1: Objective-based total internal reﬂection velocimetry (TIRV) system.

penetration depth. The penetration depth, which characterizes the length scale of the evanescent

ﬁeld, can be calculated from

p =

λ

0

4π

_

n

2

1

sin

2

θ −n

2

2

_

−

1

2

, (4.2)

where n

1

and n

2

are the indices of refraction of the solid boundary and liquid, respectively. However,

a variety of factors, including statistical variations in illumination intensity, quantum eﬃciency of

the imaging system and, most importantly, non-uniformity of the particle sizes, can lead to varia-

tions in the observed ﬂuorescent intensities of an ensemble of nominally identical particles. Thus,

a statistical analysis is carried out by characterizing these variations through a single parameter

r, or eﬀective emission radius, with which a joint probability density function (PDF), P (h, I

e

), of

the particle distance to the solid surface and emitted ﬂuorescent intensity can be obtained.

If near-wall velocities of a pure ﬂuid are to be measured by tracking motions of tracer particles,

it is important to recognize that shear and near-surface hydrodynamic eﬀects can cause a tracer

particle to rotate and translate at a velocity, U, lower than the velocity of the local ﬂuid element in

the same shear plane [12, 38, 60]. Factors that determine the particle translation velocity include

particle radius, a, particle distance to the solid surface, h, and the local ﬂuid shear rate, S (h).

Therefore corrections need to be made when one convert ﬂuid velocities into particle velocities. It

should be noted that in the presented analysis, the corrected particle translation velocity does not

account for the possibility of slip between the ﬂuid and the tracer particle, and thus any calculation

based on U represents a no-slip case.

Because tracer particles are used to probe near-surface shear ﬂow, assurance is needed that the

particle ensemble uniformly samples all shear layers. It has been suggested that shear-induced lift

can be a source of particle migration away from the solid wall [86]. However, based on the theory

presented by Cherukat & McLaughlin [87], the shear-induced lift under the presented experimental

conditions is insigniﬁcant, and thus alleviating this concern (see Appendix B).

The ensemble-averaged velocity,

¯

U, of a large number of uniformly distributed particles emitting

in an intensity range of α < I

e

< β and located in an imaging range of h

1

< h < h

2

, can be

calculated by

¯

U =

1

h

2

−h

1

_

h

2

h

1

U (h, a, S (h)) P(h, α < I

e

< β) dh. (4.3)

Because equation (4.3) is based on a no-slip boundary condition, if there exists a slip velocity, U

slip

,

41

at the liquid/solid substrate interface, the same particle ensemble will exhibit an apparent velocity

of

¯

U

app

= U

slip

+

¯

U = δ ˙ γ

w

+

¯

U, (4.4)

where U

slip

is characterized as the product of the slip length, δ, and the wall shear rate, ˙ γ

w

. It

should be noted that

¯

U

app

can be experimentally measured by ﬁnding an ensemble-averaged velocity

of “trackable” tracer particles while ˙ γ

w

is computed from ﬂow rate and channel geometry. With

¯

U

calculated by using equation (4.3), one slip length can be obtained for each wall shear rate.

Monodispersed Fluorescent Polystyrene Microspheres (Duke Scientiﬁc) with diameters of 100

(±10%) and 200 nm (±5%) suspended in puriﬁed water (Fluka) at 0.005-0.04% volume fraction

were used as tracer particles in this experiment. These microspheres have a peak absorption

wavelength of 542 nm and emit at 612 nm. Prior to each experiment, the ﬂuid was degassed

by placing the solution in vacuum for at least 30 minutes. This procedure has been reported to

signiﬁcantly eliminate nanobubble formation [83], which could be an alternative source of apparent

slip [7, 34, 82].

Test channels were fabricated using a polydimethylsiloxane (PDMS) (Dow Corning Sylgard 184)

molding technique [69] and bonded onto polished glass wafers. The dimensions of the test channels

were 50 ± 1 µm deep, 250 ± 1 µm wide and 15 mm long. Hydrophilic and hydrophobic microchan-

nels were created by oxygen plasma treatment of the PDMS mold and by bonding untreated PDMS

channels onto octadecyltrichorosilane(OTS)-coated glass wafers, respectively. The hydrophilic and

hydrophobic glass surfaces had an RMS surface roughness of 0.47 nm and 0.35 nm respectively.

A continuous-wave 514-nm Argon-ion laser beam (Coherent) was directed through a Nikon PL

Apo NA 1.45 100X TIRF oil immersion objective at an angle that created total internal reﬂection at

a glass-water interface, thus illuminating the near-surface region of water with an evanescent ﬁeld

(ﬁgure 4.1). Fluorescent images of near-surface particles were captured by a Q-Imaging Intensiﬁed

Retiga CCD camera (ICCD). Approximately 1000 images were captured at each ﬂow rate. The

ﬂows were driven by a Harvard Apparatus 22 syringe pump, with special attention paid to removing

pulsations and maintaining steady pumping motions. Detailed description and schematics of the

experimental setup have been presented in [85].

The analysis of particle image pairs was performed using a custom particle-tracking algorithm.

In summary, velocimetry analysis started with ﬁnding the positions and peak intensities of all

particles via threshold-identiﬁcation and Gaussian ﬁtting of the intensities of the pixels surrounding

the peak. Subsequently each particle’s displacement was obtained with a limited-range nearest-

neighbor matching. Finally, particles within a desired intensity range were selected for each ﬂow

rate and their mean streamwise velocity was deﬁned as the apparent velocity of the ensemble and

compared to theoretical no-slip values. Slip lengths were then obtained based on equation (4.4).

Figure 4.2 shows the measured slip lengths of aqueous solutions under various experimental

parameters. The ﬁrst observation to be made is that all measurements report slip lengths of

approximately 100 nm or less. These results further conﬁrm previously reported measurements

[25, 26, 31, 85] that there is minimal slip over smooth solid surfaces. Slip on a hydrophobic surface

appears to be slightly higher than on a hydrophilic surface. A quantitative comparison of all

measurements shows that the slip length attributed to surface hydrophobicity averages to 22 nm at

the tested shear rates. The additional slip caused by surface hydrophobicity is in agreement with

many experimental results [25, 26, 28, 31], but is in sharp disagreement with some others [30, 33].

Electrokinetic eﬀects [35] and electrostatic repulsion between tracer particles and glass surface

[7] have both been proposed as sources that might cause an apparent slip and could aﬀect the

accuracy of slip velocity measurements. Their signiﬁcance, however, is expected to decrease with

increasing ionic strength of test ﬂuids. Lauga [35] suggested that for an aqueous solution with 1

42

0 500 1000 1500 2000

0

50

100

150

Wall Shear Rate (1/sec)

A

p

p

a

r

e

n

t

S

l

i

p

L

e

n

g

t

h

(

n

m

)

200−nm, DI−water, Hydrophilic

200−nm, DI−water, Hydrophobic

200−nm, 0.1mM NaCl, Hydrophobic

200−nm, 1mM NaCl, Hydrophobic

100−nm, DI−water, Hydrophobic

Figure 4.2: Measured slip lengths of aqueous solutions. The error bar on each data point repre-

sents a 95% conﬁdence interval of each ensemble calculation. The uncertainty of each slip length

measurement (not drawn for plot clarity) is less than 20 nm, estimated based on penetration depth

calibration and particle radius variation [85]. Data of “200-nm, DI-water, Hydrophilic” and “200-

nm, DI-water, Hydrophobic” have been previously reported by Huang et al.

mM NaCl concentration, the apparent slip length would become sub-molecular. As shown in ﬁgure

4.2, variations in aqueous ionic concentration do not change measured slip lengths signiﬁcantly.

This observation suggests that the measured slip lengths are most likely not due to ionic eﬀects,

but are consequences of true boundary slip.

Another important observation is that the slip lengths do not vary signiﬁcantly over the tested

range of shear rates. This observation agrees with experimental studies conducted under similar

ranges of moderate shear rates [28, 29, 31]. Still, this result does not suggest that slip length is

independent of shear rates, as the conducted measurements span only one order of magnitude of

shear rates. Zhu & Granick [26], Neto et al. [27] and Choi et al. [25] all tested over larger ranges

of shear rates (> 2 orders of magnitude) and reported shear-dependent slip lengths. It is physically

plausible that the shear dependence of slip length is nonlinear and the shear eﬀect is signiﬁcant

only at higher shear rates. To assess this, a TIRV system equipped with a very sensitive high-speed

camera would be needed for measurements at high shear rates.

Chapter 5

Paper 4: Direct measurement of

anisotropic near-wall hindered

diﬀusion using total internal reﬂection

velocimetry

By applying the three-dimensional total internal reﬂection velocimetry (3D-TIRV) technique to

freely suspended micron-sized ﬂuorescent particles, we aim to simultaneously observe the three-

dimensional anisotropic hindered diﬀusion for gap-size-to-radius ratio much less than one. We

demonstrate that the three-dimensional tracking technique of TIRV used for nanoparticles can be

adopted into 3D displacement measurements of freely suspended 1.5-µm radius particles. The dis-

placement measurements reveal that the hindered diﬀusion coeﬃcients are in close agreement with

the theoretical values predicted by the asymptotic solutions of Brenner [36] and Goldman et al. [37]

for gap-size-to-radius ratio much less than one, and hindered diﬀusion anisotropicity is simultane-

ously observed in all data sets.

5.1 INTRODUCTION

Advancement in colloidal sciences have lead to many applications of micro- and nano-particles in

engineering research (eg. particle imaging velocimetry) and biotechnology (eg. drug delivery). At

these length scales Brownian motions are signiﬁcant and understanding these thermal agitations

are essential in making practical use of these tiny particles. Inside a ﬂuid bulk the diﬀusivity of

an isolated particle follows the Stokes-Einstein relation, which is the ratio of ﬂuid thermal energy

to the particle’s hydrodynamic mobility. In the presence of a nearby solid boundary, however, a

particle would experience an increased, anisotropic drag which hinders its mobility. Brenner [36]

and Goldman et al. [37] were the ﬁrst to developed drag force correction factors for near-wall

spheres under no inertial eﬀects and a no-slip boundary condition. These correction factors have

since evolved into theories of hindered diﬀusion [88].

Following these works, many experimental studies have been conducted to observe hindered dif-

fusion and to verify the correction factors. Demonstrated experimental techniques include evanes-

cent light-scattering [39, 40, 42], total internal reﬂection ﬂuorescence microscopy (TIRFM) [43, 44]

and combined optical tweezers and digital video microscopy [41]. In most of the above mentioned

studies, simultaneous three-dimensional measurements of the anisotropic diﬀusivity could not be

43

44

conducted due to experimental limitations. One exception is a ratiometric-TIRFM measurement

conducted by Banerjee & Kihm [43], who reported anisotropic diﬀusivities that only partially agree

with the theories, probably due an inaccurate accounting of particle positions. Another exception

is a study reported by Lin et al. [41], who demonstrated that the anisotropic hindered diﬀusion

could extend far away from the wall.

In the theories of Brenner and Goldman et al. the hindered mobility of a near-wall particle is

a function of the particle’s radius, a, and the gap size between the particle and the wall, h. They

proposed analytical solutions of the hindered mobility that are vastly diﬀerent for h/a 1 and

for h/a ¸ 1. Based on our literature survey, no study has demonstrated the anisotropic hindered

diﬀusion for h/a ¸ 1 with a simultaneous three-dimensional measurement as studies of Banerjee

& Kihm and Lin et al. both attempted to measure hindered diﬀusion at h/a 1. In this paper we

present our experimental study aimed to validate the anisotropic mobility correction coeﬃcients for

h/a ¸1 through a direct measurement of hindered diﬀusion using three-dimensional total internal

reﬂection velocimetry (3D-TIRV).

5.2 THEORY OF HINDERED DIFFUSION

When an isolated particle is at the vicinity of a solid boundary, its Brownian motion is hindered

due to an increase in hydrodynamic drag. The presence of the solid wall also breaks the symmetry

of particle dynamics, resulting in anisotropic Brownian motion. Brenner [36] successfully solved

the lubrication equation of particle motion normal to the solid wall and proposed an inﬁnite series

solution of the drag correction factor, β

⊥

. He reported that the correction factor is a function of

the particle radius, a, and the gap size between the particle and the solid wall, h. Later Bevan &

Prieve [39], using a regression method, reported that

β

⊥

≡

D

⊥

D

0

≈

6h

2

+ 2ah

6h

2

+ 9ah + 2a

2

(5.1)

is a close approximation to Brenner’s inﬁnite series solution. For the diﬀusivity correction factor in

the direction parallel to the solid wall, β

**, an exact analytical solution was never found. Instead,
**

Goldman et al. [37] oﬀered an asymptotic solution,

β

≡

D

D

0

= −

2

_

ln

_

h

a

_

−0.9543

¸

_

ln

_

h

a

_¸

2

−4.325 ln

_

h

a

_

+ 1.591

, (5.2)

for particles very close to the wall, deﬁned by h/a ¸1.

5.3 EXPERIMENTAL PROCEDURES

To experimentally verify equations (5.1) and (5.2), diﬀusion of micron-sized ﬂuorescent particles in

an evanescent ﬁeld was tracked with digital imaging microscopy. The technique, termed 3D-TIRV,

have been demonstrated by Huang et al. in measuring motions of near-wall nanoparticles [89].

Unlike evanescent light-scattering experiment of non-ﬂuorescent particles, TIRV allows particle

centers to be identiﬁed on the captured ﬂuorescent images, and consequently particle motions

can be tracked via the displacements of particle centers. In addition, ﬂuorescent intensity of the

particles can be used to infer the instantaneous separation distance between the particle and the

two-media interface, as commonly done in traditional TIRFM experiments [44, 90].

45

θ

z

x

water (n = 1.33)

glass (n = 1.51)

~ penetration depth

Figure 5.1: Schematic of TIRV. A red ﬂuorescent microparticle suspended in water is placed in

a green evanescent ﬁeld created within the focal depth of a high numerical aperture microscopy

objective. A collimated laser beam through the objective is used as the illumination light source.

At the illumination beam incident angle, θ, greater than 61.9

◦

, total internal reﬂection occurs at the

glass/water interface. Because the particle radius is much larger than the evanescent penetration

depth, the evanescent energy illuminates only the lower portion of the encapsulated ﬂuorophores.

Our 3D-TIRV setup was created on an inverted epi-ﬂuorescent microscope (Nikon TE-2000). A

continuous-wave, collimated 514-nm Argon-ion laser beam was directed through a Nikon PL Apo

NA 1.45 100X TIRF oil immersion objective at an angle that created total internal reﬂection at

a glass/water interface. The water phase was an aqueous solution consisted of 10mM NaCl and

individual 1.5µm-radius (±5%) ﬂuorescent polystyrene particles (refractive index 1.59, Spherotec

Inc.) suspended at 0.02% volume fraction. The low volume fraction, and thus low particle number

density, ensured the isolated-particle assumption of the theories was met. Before each measurement

the solution was sonicated in intervals of 30 seconds for 10 minutes to disperse coagulated particles.

For image acquisition, 200 µL of the solution was injected into a closed reservoir formed by a piece

of carved polydimethylsiloxane (PDMS) sandwiched between glass coverslips. Subsequently TIRV

imaging of hindered particle Brownian motions was performed at one of the glass/solution interface.

The ﬂuorescent images of the particles were projected onto a Q-Imaging Intensiﬁed Retiga CCD

camera (ICCD), and recorded at a 10-Hz frequency. Overall, 2000 to 2500 sample images were

captured for each experiment for reliable statistics.

A particle’s 3D position was determined through threshold-identiﬁcation and Gaussian ﬁtting of

the intensities of the pixels surrounding the peak. This method has been previously demonstrated

in TIRV with nanoparticles. Still, a calibration experiment was necessary to verify its validity for

1.5-µm particles, especially in determining the relationship between the particle/wall gap size and

the particle’s peak ﬂuorescent intensity. To do so, individual 1.5-µm radius ﬂuorescent polystyrene

particles were attached to polished conical tips of thin graphite rods. By mounting the assembly to

a 0.4-nm precision translation stage, the ﬂuorescent particles were traversed through the evanescent

ﬁeld and their ﬂuorescent images were digitally captured at various distances to the glass surface.

The result of this calibration is shown in ﬁgure 5.2. The close agreement between particle intensity’s

exponential decay length and the evanescent ﬁeld penetration depth suggests that particle-glass gap

size can be reliably inferred from the particle peak intensity. We also found that the precision of

center identiﬁcation was approximately 0.5 pixels, or 32 nm.

46

0 50 100 150 200 250 300

0

0.2

0.4

0.6

0.8

1

Gap size, h (nm)

I

/

I

0

Particle 1

Particle 2

Particle 3

Exp. fit (d = 142 nm)

Figure 5.2: Gaussian-ﬁtted peak intensities, I, of 1.5-µm radius ﬂuorescent particles in evanescent

ﬁeld, taken at 0 to 275 nm away from the glass surface. I

0

is the ﬁtted intensity at h = 0. Each data

point represents the particle peak intensity averaged over 10 images, while the length of the error

bar spans two standard deviations. The laser incident angle is 64

◦

and the resulting evanescent

ﬁeld penetration depth is 148 nm. All data series exhibit an exponential decay tendency versus

gap size. With an exponential decay length of 142 nm, the best ﬁt of the intensity data shows close

agreement to the penetration depth.

Once positions of all imaged particles were determined, particle displacements were calculated

between consecutive frames. The hindered diﬀusion coeﬃcient in the direction parallel to glass

surface, D

**, was calculated from the equation
**

¸∆R)

2

= πD

∆t (5.3)

where ∆R is the averaged radial displacement of particles, ∆t is the time between consecutive

image acquisitions (= 100 millisecond), and ¸) represents ensemble average. Similarly, the hindered

diﬀusion coeﬃcient in the direction normal to glass surface, D

⊥

, was calculated from

¸(∆z)

2

) −¸∆z)

2

= 2D

⊥

∆t (5.4)

where ∆z is the particle displacement normal to the glass surface. Finally, to obtain the hindered

diﬀusion correction factors, β

and β

⊥

, diﬀusion coeﬃcient of the same 1.5-µm particles were

measured in the ﬂuid bulk, using regular ﬂuorescent digital microscopy.

5.4 RESULTS AND DISCUSSION

Shown in ﬁgure 5.3 are hindered diﬀusion correction factors measured by 3D-TIRV. In addition to

experimental results, hindered diﬀusion coeﬃcients from a Brownian dynamics simulation [89] are

also plotted for comparison. These results are compared to the asymptotic solution of Goldman et

47

0 0.05 0.1 0.15 0.2

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

h/a

D

/

D

0

GCB

MOR

Bevan

D

X

(Sim.)

D

Z

(Sim.)

D

X

(Exp.#1)

D

Z

(Exp.#1)

D

X

(Exp.#2)

D

Z

(Exp.#2)

Figure 5.3: Hindered diﬀusion correction factor (D

x

/D

0

, D

z

/D

0

) vs. non-dimensional gap size

between particles and glass surface (h/a). D

0

is the diﬀusion coeﬃcient measured in the ﬂuid

bulk while D

x

= D

and D

z

= D

⊥

. Each data point is obtained from an ensemble of particles

found within ±0.005 or ±0.01 of the targeted gap size values. “GCB”, “MOR” and “Bevan” repre-

sent asymptotic solution of Goldman et al., the Bevan approximation and “Method of Reﬂection”

solution, respectively. “Exp.” represents experimental data while “Sim.” means data obtained

from Brownian dynamics simulation. Each error bar represents the 95% conﬁdence interval of

measurement.

al. (equation (5.2)), Bevan’s approximation (equation (5.1)) and a “Method of Reﬂection” (MOR)

solution [37]. Theoretically equation (5.2) is more appropriate for the measured gap sizes of h/a ¸1

while the method of reﬂection solution is more accurate at h/a > 1, but nevertheless they are both

plotted for a quantitative comparison. The correction factor in the direction parallel to glass surface,

β

≡ D

x

/D

0

, increases from approximately 0.2 at h/a ≈ 0 to 0.4 at h/a ≈ 1.3, while the correction

factor in the direction normal to glass surface, β

⊥

= D

z

/D

0

, increases from 0 to 0.1 in the same

h/a range, demonstrating the anisotropicity of near-wall hindered diﬀusion. It is observed that the

measured β

**values at h/a < 0.05 are very close to that predicted by equation (5.2) but signiﬁcantly
**

deviate from the MOR solution, conﬁrming the validity of the asymptotic solution at h/a ¸ 1.

The transition from the asymptotic solution to the method of reﬂection solution is demonstrated

at h/a > 0.1 as the measured β

**values fall between the two solutions. The measured β
**

⊥

agrees

well with Bevan’s approximation, except at 0.05 < h/a < 0.1 where measured β

⊥

is slight larger

than the predicted values possibly due to insuﬃcient or slightly biased particle sampling. A close

agreement between the measured and the predicted β

⊥

values at extremely small h/a has also been

reported by Oetama & Walz [42], who conducted one-dimensional hindered diﬀusion measurement

in the range h/a < 0.025. Finally, the experimental data also agree well with the simulation results,

conﬁrming the validity of our measurement technique.

As in most near-wall colloidal measurements, we realize the importance of recognizing other

acting physical forces that could lead to measurement inaccuracy. One of these forces is gravitational

48

pull or sedimentation of the particles. At a ﬁrst glance, it is perceivable that sedimentation could

lead to bias in diﬀusion measurement normal to the glass boundary. In the ﬂuid bulk of density ρ

f

and dynamic viscosity µ, the terminal settling velocity, w

s

, of a particle with radius a and density

ρ

p

is

w

s

=

2 (ρ

p

−ρ

f

) ga

2

9µ

, (5.5)

where g is the gravitational acceleration. For a 1.5-µm radius polystyrene particle of density 1050

kg/m

3

, this terminal settling velocity would be 245 nm/sec, equivalent to a settling displacement

of 24.5 nm during the imaging inter-frame time of 0.1 seconds. However, when the particle ap-

proaches the solid boundary, its terminal velocity is expected to decrease with a correction factor

identical to β

⊥

for the same hydrodynamic reason of decreased mobility. Based on equation (5.1),

within the evanescent penetration depth the particles would settle for a distance of less 2.45 nm

in the inter-frame time of 0.1 seconds, or equivalently a non-dimensional gap size of 0.0016 for

our measurement gap size of h/a < 0.14. Therefore in the time scale of our Brownian motion

measurements, sedimentation can be considered as a negligible factor.

Besides hydrodynamic interaction, electrostatic repulsion can also exist between the polystyrene

particles and the glass surface as they both carry negative surface charges when immersed in

aqueous solution [51]. Indeed when the same ﬂuorescent particles were suspended in de-ionized

water and observed under evanescent wave imaging, we found few particles came close to glass

surface. However the length scale of electrostatic repulsion can be easily decreased by increasing

the electrolyte concentration of the suspending aqueous solution. By adding 10 mM of NaCl to the

solution, we decreased the electric double layer thickness surrounding the particles and the glass

surface to a Debye length ∼ 3 nm, or h/a ∼ 0.002, and thus signiﬁcantly reduced the eﬀect of

electrostatic repulsion.

Another colloidal force that could potentially aﬀect measurement accuracy is van der Waals

force between the particles and the glass. However, for a particle/glass gap size of 10 nm and

greater, van der Waals force scales with h

−3

[91], making its eﬀective range even shorter than that

of electrostatic repulsion. Thus it is safe to assume that van der Waals force is also insigniﬁcant

for the range of h/a under consideration.

The hydrodynamic mobility correction factors proposed by Brenner and Goldman et al. assume

a no-slip boundary condition at particle surfaces. If ﬂuid slip exists at the particle surfaces, it

is expected that the theories of Brenner and Goldman et al. would under-estimate near-surface

particle mobility and the hindered diﬀusion coeﬃcients. Several recent theoretical and experimental

studies, however, oﬀer insights into whether slip eﬀect should be taken into consideration. First,

by conducting slip measurements of water ﬂowing over hydrophobic surfaces, Zhu & Granick [26]

concluded that apparent slip lengths are only a few nanometers if the rms surface roughness is

3.5 nm or larger. Because the polystyrene microspheres used in the current hindered diﬀusion

experiment are hydrophilic and have surface roughness of at least 10 nm [92], the eﬀective slip

length at particle surfaces, δ, is expected to be of only a few nanometers in magnitude, if not sub-

nanometer. Thus under the current experimental conditions, h/δ ¸ 10. Consequently, based on

the theory of particle mobility presented by Vinogradova [93], slip of such magnitude would have an

insigniﬁcant eﬀect on the particle mobility for the particle diameter and particle-wall gap size under

consideration. Therefore the no-slip assumption is considered valid in the current experiment, and

is additionally veriﬁed by the agreement between experimental data and theoretical values shown

in ﬁgure 5.3.

49

5.5 SUMMARY

A direct measurement of hindered diﬀusion was conducted with total internal reﬂection velocimetry.

We believe that this is the ﬁrst simultaneous three-dimensional measurement of hindered diﬀusion

coeﬃcients for h/a ¸ 1. The anisotropic characteristic of hindered diﬀusion is experimentally

conﬁrmed and the correction factors are found to agree with the theories of Brenner and Goldman

et al. The results conﬁrm the increase of hydrodynamic drag when a particle approaches a solid

boundary, and such correction shall be applied to not only diﬀusion but also other translational

motion of particles where the drag force is of concern.

Chapter 6

Paper 5: Simulations of hindered

diﬀusion in shear ﬂow and its

implications for near-wall velocimetry

The ensemble behaviors of near-surface particles in a shear ﬂow, and the eﬀects of the wall presence

and hindered diﬀusion on the measured apparent velocities are explored through Brownian dynamics

simulations with diﬀusive time and particle radius as time and length scales, respectively. It is

observed that the shear force dominates over diﬀusion at Pe > 3, and asymmetric shape and width

of apparent velocity distributions are attributed to the shear eﬀect. It is also found that if the

time interval between successive particle image acquisitions is short, an under-estimation of ﬂuid

velocity can result from biased sampling of tracer particles very close to the wall. However, if the

time interval between successive particle image acquisitions is long, a signiﬁcant portion of the

tracer particles would sample planes of higher velocities, resulting in an over-estimation of overall

ﬂuid velocity. Particle drop-in’s and drop-out’s, are found to be a potential source of measurement

error for nano-PIV because of the rapid Brownian motion of nanoparticles. The combined eﬀect

of the observations described above is that near-wall particle-based velocimetry measurement is not

time-invariant. Still, the results found in the Brownian dynamics simulation oﬀer a way where the

true ﬂuidic velocities can be inferred from particle apparent velocities through proper scaling. This

scaling method, however, is available only for TIRV but not for nano-PIV, making TIRV the more

superior method in near-surface measurements.

6.1 INTRODUCTION

Colloidal particle-based image velocimetry has long been used as an experimental method in mea-

suring ﬂuid velocity proﬁle and other physical quantities. Its accuracy heavily relies on the assump-

tion that tracer particles will accurately trace local ﬂuid velocities. In the past decade, particle

image velocimetry (PIV) has been extended to the micro- [55] and nano-scale [56] where size of

tracer particles has also decreased from microns to nanometers. At these physical length scales,

Brownian motion of tracer particles can be quite signiﬁcant, thus violating the assumption of par-

ticles travelling at velocities equal to that of the surrounding ﬂuids. Consequently, conducting an

accurate velocimetry experiment requires a good understanding and a careful treatment of Brow-

nian motion via either a thorough error analysis [55], an ensemble correlation averaging technique

[54], a statistical analysis of the particle ensemble [80, 85] or a method of statistical tracking [94].

50

51

In the vicinity of a solid wall, a colloidal particle will undergo a “hindered” Brownian motion

due to an lubricational increase of its hydrodynamic drag. This is known as hindered diﬀusion and

has been reported both theoretically [12, 36, 37, 38] and experimentally [39, 41, 42, 43, 95]. In most

cases, such a spatially dependent Brownian motion would lead to greater diﬃculties in accessing

measurement uncertainties. Only a few researchers managed to turn the disadvantages into merits

by proposing usage of the extent of hindering to reconstruct near-wall shear ﬂow velocity proﬁle

[96] and to probe the no-slip boundary condition [97].

To study the ensemble behavior of hindered and non-hindered Brownian motions, there are

two equally appropriate approaches [58]. One is the Fokker-Planck approach, which solves the

momentum-space partial diﬀerential equations to obtain a time evolution of spatial conﬁguration

function of the particle ensemble. Recently, Sadr et al. [59] had taken the Fokker-Planck approach

to study the hindered diﬀusion of particles in the direction normal to the wall and its eﬀect on

the bias of velocimetry. The other approach is a Brownian dynamics (BD) simulation, which is

to simulate motion of each particle in a large ensemble through a stochastic diﬀerential equation.

In this approach, both deterministic (such as ﬂuid ﬂow and sedimentation) and stochastic (such

as Brownian motion) processes contribute to particle displacements. The grand simulation then

yields a spatial distribution of the particle ensemble after each time step. Details provided by this

method are not only intuitive in understanding ensemble behavior but also bear a close resemblance

to physical velocimetry experiments.

The usefulness of BD simulations has been demonstrated in studying the impact of hindered

Brownian diﬀusion on the accuracy of nano-PIV [63], on the colloidal particle deposition in a

microchannel ﬂow [61], and on the accuracy of potential energy proﬁles determined via total internal

reﬂection microscopy [62]. What has yet to be examined is the eﬀect of hindered diﬀusion and the

presence of the wall on the accuracy of velocimetry. In addition, it would be of interest to examine

how the relative strength of hindered diﬀusion and shear ﬂow leads to skewed near-wall apparent

velocity distributions ﬁrst reported by Jin et al. in their total internal reﬂection velocimetry (TIRV)

experiment [80], and the relationship between particle diﬀusion, time between image acquisitions

and the accuracy of velocity measurements based on ensemble averages. In this paper the theories

of near-wall particle dynamics will ﬁrst be presented and followed by a detailed description of

the BD simulation algorithm. We then discuss the simulation results and their implications, and

conclude with a summary and our thoughts on the accuracies of various velocimetry methods.

6.2 THEORIES AND COMPUTATIONS

6.2.1 The Langevin Equation

In Brownian dynamics simulation, particle displacements are computed based on a stochastic

Langevin equation [58]. For a particle in a shear ﬂow as shown in ﬁgure 6.1, its displacement

between simulation time step i and step i + 1 with a step size δt is,

x

i+1

−x

i

= Uδt +

dD

x

dx

δt +

D

x

k

B

Θ

F

x

δt +N

_

0,

_

2D

x

δt

_

, (6.1a)

z

i+1

−z

i

=

dD

z

dz

δt +

D

z

k

B

Θ

F

z

δt +N

_

0,

_

2D

z

δt

_

, (6.1b)

where (x

, z

**) is the particle’s center position, k
**

B

is the Boltzmann constant and Θ is the ﬂuid

temperature. D

x

and D

z

are the diﬀusion coeﬃcients in the directions parallel and normal to the

solid surface, respectively. In the ﬂuid bulk, both D

x

and D

z

would be equal to the Stoke-Einstein

52

Solid

z

x

a

z’

x’

S

U

Fluid

Figure 6.1: A schematic of the simulation geometry. A colloidal particle of radius a is freely

suspended in a ﬂuid but near a solid boundary. The ﬂuid is undergoing a shear ﬂow of shear rate

S, and thus the particle translates due to both ﬂuid ﬂow and its Brownian motion. A no-slip

boundary condition is assumed at the ﬂuid/solid interface. Even though existence of slip has been

reported [85], its presence would not alter the simulation results and is thus neglected.

diﬀusivity, D

0

. As it has been mentioned earlier, near-wall diﬀusion is anisotropic and hindered,

and thus D

x

< D

0

and D

z

< D

0

. It should be noted that because D

x

is only a function of z

,

dD

x

/dx

= 0 in equation (6.1a). The z

-dependency of D

x

and D

z

is discussed in section 6.2.3.

F

x

and F

z

represent external forces acting on the particle in the x- and z-directions, respectively,

and N

_

0,

√

2Dδt

_

denotes the stochastic displacement of Brownian motion randomly sampled

from a normal distribution with a zero mean and a standard deviation

√

2Dδt. In the current

BD simulation scheme there exists no force in the x-direction and F

x

= 0. Density mismatch

between tracer particles and the suspending ﬂuid, on the other hand, leads to either sedimentation

or ﬂoatation of the particles. The gravitation sinking force acting on the particles, F

g

, is thus the

only external force in the z-direction and

F

g

=

4π

3

a

3

∆ρg, (6.2)

where ∆ρ is the density diﬀerence between the tracer particles and the suspending ﬂuid, and g is

the gravitational acceleration.

The equations of motion (6.1a) and (6.1b) are non-dimensionalized by choosing the particle

radius, a, as the length scale and time required for the particle to diﬀuse a distance of one radius,

a

2

/D

0

, as the time scale. Therefore equations (6.1a) and (6.1b) become

X

i+1

= X

i

+F

_

Z

i

_

Pe Z

i

δT +N

_

0,

_

2β

x

(Z

i

) δT

_

(6.3a)

and

Z

i+1

= Z

i

+

dβ

z

dZ

¸

¸

¸

¸

Z

i

δT +G β

z

_

Z

i

_

δT +N

_

0,

_

2β

z

(Z

i

) δT

_

(6.3b)

53

S = 10

0

sec

−1

10

1

sec

−1

10

2

sec

−1

10

3

sec

−1

G =

a = 100 nm Pe = 0.0046 0.0463 0.4630 4.630 −5.042 10

−5

a = 1 µm 4.630 46.30 463.0 4630 -0.5042

Table 6.1: Sample values of the Peclet number, Pe, and sedimentation coeﬃcient, G.

∆t = 0.1 msec ∆t = 1 msec ∆t = 10 msec ∆t = 100 msec

a = 100 nm 0.022 0.22 2.2 22

a = 1 µm 0.000022 0.00022 0.0022 0.022

Table 6.2: Representative values of the non-dimensional time between consecutive image acquisi-

tion, ∆T.

where X

≡ x

/a, Z

≡ z

/a, and T ≡ D

0

t/a

2

are the non-dimensional x

, z

**and t, respectively and
**

F

_

Z

_

≡

U

z

S

, β

x

_

Z

_

≡

D

x

(z

)

D

0

, β

z

_

Z

_

≡

D

z

(z

)

D

0

as described in sections 6.2.2 and 6.2.3 while

Pe ≡

Sa

2

D

0

, G ≡

4πa

4

g∆ρ

3k

B

Θ

.

The Peclet number, Pe, represents the relative strength of shear force and diﬀusion, and the

sedimentation coeﬃcient, G, characterizes the gravitational pull on the particles. Representative

values of Pe and G are shown in table 6.1.

In image-based velocimetry measurements, another important control parameter is the time

between consecutive image acquisitions, ∆t. Some sample values of non-dimensional time between

consecutive image acquisition, ∆T, for 1-µm and 100-nm particles are shown in table 6.2.

6.2.2 Eﬀects of Shear on Particle Velocities

It is well known that shear and near-surface hydrodynamic eﬀects can cause a tracer particle to

rotate and translate at a velocity lower than the local ﬂuid velocity in the same shear plane [12, 38].

Goldman et al. [38] proposed that the translational velocity, U, of a particle with radius a in a

shear ﬂow of a local shear rate S is given by

U

z

S

≡ F

_

Z

_

· 1 −

5

16

_

Z

_

−3

, (6.4)

which is valid for large Z

, and

U

z

S

≡ F

_

Z

_

·

0.7431

0.6376 −0.2 ln (Z

−1)

(6.5)

for small Z

. Although there exists no analytical approximation for intermediate values of Z

,

Pierres et al. [60] proposed a cubic approximation to numerical values presented by Goldman et

al. in [38]:

U

z

S

≡ F

_

Z

_

·

_

1

Z

_

exp

_

0.68902 + 0.54756

_

ln

_

Z

−1

_¸

+0.072332

_

ln

_

Z

−1

_¸

2

+ 0.0037644

_

ln

_

Z

−1

_¸

3

_

.

(6.6)

54

Because a particle’s translational velocity depends on the shear rate and the distance to the wall,

it needs to be updated in equation (6.1a) at every time step of the simulation.

It has also been suggested that shear-induced lift can be a source of particle migration away

from the wall [86]. However, based on the theory presented by Cherukat & McLaughlin [87], the

shear-induced lift is insigniﬁcant for micro- and nano-particles in a low shear ﬂow regime, and thus

will be neglected (for details, see Appendix B).

6.2.3 Hindered Diﬀusion

Near-wall tracer particles are known to exhibit anisotropic hindered Brownian motion due to hy-

drodynamic eﬀects, and their hindered diﬀusion coeﬃcient in the direction parallel to the solid

surface, D

x

, is [37]

D

x

D

0

≡ β

x

_

Z

_

= 1 −

9

16

_

Z

_

−1

+

1

8

_

Z

_

−3

−

45

256

_

Z

_

−4

−

1

16

_

Z

_

−5

+O

_

Z

_

−6

, (6.7)

where D

0

is the Stokes-Einstein diﬀusivity of an isolated spherical particle in the ﬂuid bulk. This

“Method of Reﬂection” approximation is more accurate for Z

> 2. For Z

< 2, Goldman et al.

[38] proposed an asymptotic solution,

D

x

D

0

≡ β

x

_

Z

_

= −

2 [ln (Z

−1) −0.9543]

[ln (Z

−1)]

2

−4.325 ln (Z

−1) + 1.591

. (6.8)

In the direction normal to the wall, the modiﬁed diﬀusion constant, D

z

, is such that [36]

D

z

D

0

≡ β

z

_

Z

_

=

_

4

3

sinh α

∞

n=1

n(n + 1)

(2n −1) (2n + 3)

_

2 sinh (2n + 1) α + (2n + 1) sinh 2α

4 sinh

2

_

n +

1

2

_

α −(2n + 1)

2

sinh

2

α

−1

__

−1

,

(6.9)

where α = cosh

−1

(Z

**). Bevan & Prieve [39] reported that the equation
**

β

z

_

Z

_

=

6 (Z

−1)

2

+ 2 (Z

−1)

6 (Z

−1)

2

+ 9 (Z

−1) + 2

(6.10)

well approximates equation (6.9) and is much less computationally intensive than the inﬁnite series.

Like the particle translational velocity, the dependence of these hindered diﬀusion coeﬃcients on

Z

**requires them to be updated at every time step of the simulation.
**

6.2.4 Implementation of Simulation

Since the experiments are conducted using dilute suspensions, the BD simulations were conducted

under an assumption of no particle-particle hydrodynamic interactions. At the beginning of each

simulation, a particle was situated at X

**= 0 and randomly placed in a pre-determined range of
**

1 < Z

**< 10. The simulation then progressed for a total of ∆T/δT steps as prescribed by equations
**

(6.3a) and (6.3b), with F and β’s updated and the position (X

, Z

**) of the particle recorded after
**

each time step. Because the solid wall was located at Z = 0, the smallest Z

**value a particle could
**

have was Z

**= 1, where the particle would be in contact with the wall. A boundary condition
**

was needed in the event that a particle attempted to enter the solid wall during a simulation step.

55

Peters & Barenbrug [98, 99] have studied the eﬃciencies of diﬀerent boundary conditions for BD

simulations. Here we chose a simple and yet eﬀective specular reﬂection to prevent a particle from

entering the wall. With the time step taken small enough, the use of the boundary condition was

seldom triggered and less than 0.001% of the simulated displacements required applications of the

boundary condition.

The single particle simulation was then repeated 10

5

times to obtain a large ensemble. It was

also repeated for various values of parameters Pe and G to study their eﬀects. The initial positions

of particles and the seeding of our random number generator were made identical for all runs of

simulations to ensure that the diﬀerences in results found between runs were the consequences of

simulation parameters only.

Finally, it is important to mention the selection of the size of the computational time step,

δT, which has two physical constraints [58]. First, the time step must be much greater than the

particle relaxation time, mD

0

/k

B

Θ, where m is mass of one particle. In nondimensional terms it

is equivalent to

δT ¸

mD

0

2

k

B

Θa

2

∼ O

_

10

−6

_

(6.11)

for a > 100 nm. Secondly, numerical accuracy requires that the time step must be short enough

such that the diﬀusion coeﬃcients and their gradients are essentially constant during the time step

(that is, δT ¸ 1). Therefore δT was chosen to be 10

−4

, which satisﬁes both constraints and was

numerically eﬃcient.

6.3 RESULTS AND DISCUSSIONS

6.3.1 Sedimentation

Accurate particle velocimetry measurements require unbiased sampling of ﬂuid velocities by particle

ensembles. A common bias of this sort is sedimentation of particles between image acquisitions.

Shown in ﬁgures 6.2 and 6.3 are BD simulations of particle distribution for 1.5-µm and 100-nm

radius particles, respectively, sampled after various times ∆T. In the case of 1.5-µm particles, it can

be observed that the distribution started out uniformly, but evolves with time and eventually settle

into a steady, non-uniform spatial distribution after a transient period. The 100-nm particles,

on the other hand, remain dispersed through the volume at all times. In both case the ﬁnal

spatial distribution agrees with the Boltzmann distribution prediction [91]. These results are not

surprising, but do serve to validate our simulation. With sedimentation being negligible for small

particles, we concentrate on presenting results of sub-micron particle simulations, as these particles

are commonly used in micro-PIV, nano-PIV and TIRV as tracers.

6.3.2 Particle Displacement Due to Hindered Diﬀusion

The ﬁrst observation made is the displacement probability density function (PDF) of hindered

Brownian motion in the direction perpendicular to the wall, or the z-direction. It is well known

that the one-dimensional displacement PDF of an isolated particle in the ﬂuid bulk is a Normal

distribution N

_

0,

√

2D

0

∆t

_

. However, with the presence of the wall hindered diﬀusion is expected

to break the symmetry of the displacement PDF, and is demonstrated in ﬁgure 6.4. Particles that

start oﬀ farther away from the wall can diﬀuse a longer distance within a given amount of time,

as demonstrated by the wider displacement distribution widths. In addition, these displacement

PDF’s are more symmetric and collapse onto each other. The displacement PDF’s of near-wall

56

1 2 3 4 5 6 7 8 9 10

0

0.2

0.4

0.6

0.8

1

Z

P

D

F

(a)

1 2 3 4 5 6 7 8 9 10

0

0.5

1

1.5

2

2.5

Z

P

D

F

(b)

Δ T = 0

Δ T = 0.5

Δ T = 1

Δ T = 2

Δ T = 3

Δ T = 5

Δ T = 5

Δ T = 6

Δ T = 7

Δ T = 8

Δ T = 9

Δ T = 10

Boltzmann Distribution

Figure 6.2: Sedimentation of particles at G = −2.5, which is equivalent to a 1.5µm-radius

polystyrene particle (density 1050 kg/m

3

) suspended in pure water. The particles are uniformly

distributed in the volume (1 < Z

**< 10) at T = 0 and allowed to diﬀuse only within this volume.
**

PDF stands for probability density function.

57

1 2 3 4 5 6 7 8 9 10

0.04

0.06

0.08

0.1

0.12

Z

P

D

F

(a)

1 2 3 4 5 6 7 8 9 10

0.04

0.06

0.08

0.1

0.12

Z

P

D

F

(b)

T = 0

T = 0.5

T = 1

T = 2

T = 3

T = 5

T = 5

T = 6

T = 7

T = 8

T = 9

T = 10

Boltzmann Distribution

Figure 6.3: Sedimentation of particles at G = −5 10

−5

, which is equivalent to a 100nm-radius

polystyrene particle (density 1050 kg/m

3

) suspended in pure water. The particles are uniformly

distributed in the volume (1 < Z

**< 10) and allowed to diﬀuse only within this volume.
**

58

−2 −1 0 1 2

0

0.5

1

1.5

2

Z − Z

0

P

D

F

Z

0

= 1.5

Z

0

= 2

Z

0

= 6

Z

0

= 11

Z

0

= 51

Z

0

= 101

Figure 6.4: Displacement distribution of small particles from various initial positions, or Z

0

. All

particles are allowed to diﬀuse for an identical time ∆T = 0.1, during which time no particle is

able to reach the wall.

particles, on the other hand, are signiﬁcantly skewed with a more pronounced tails in the positive

values and are narrower. This observation suggests that hindered diﬀusion could lead to a bias of

measurements toward values obtained in the near-wall region.

Further proof of the hindered diﬀusion eﬀect is shown in ﬁgure 6.5. Particles start to diﬀuse

away from the initial position of Z

**= 2 as time evolves, with the spatial distribution skewed toward
**

the wall (Z = 0), which is a direct consequence of hindered diﬀusion. After long periods of time

when the particles are allowed to reach the wall through diﬀusion (∆T > 0.3), the skewness of the

spatial PDF is even more pronounced, leading to a high concentration of particles at the wall. Such

time-dependence of the particle spatial distribution could lead to time-dependent apparent velocity

measurements and is further discussed in section 6.3.5.

6.3.3 Particle Drop-in’s and Drop-out’s

The accuracy of velocimetry measurements relies on the ability to detect the same particles in

consecutive image acquisitions. This is especially diﬃcult in near-wall microscopy measurements

because near-wall sub-micron particles can diﬀuse away from the near-wall region quickly. One

such situation is demonstrated in ﬁgure 6.6. Suppose the imaging range of near-wall microscopy is

1 < Z

**< 5, which is a good estimate for evanescent wave imaging using 100-nm radius particles.
**

The particles, initially uniformly distributed within the imaging range, will start to leave the

imaging range as time evolves. The portion of the particles that are not present in the imaging

range at the second image acquisition are said to have “dropped out”. Clearly, more particles

would drop out with longer inter-acquisition time. For the overall concentration of the particles to

remain uniform, many “outside” particles would have to “drop in” to take over the space. In PIV,

images of the dropping in particles at the second image acquisition would lead to additional errors

59

1 2 3 4 5

0

0.5

1

1.5

Z

P

D

F

Δ T = 0

Δ T = 0.1

Δ T = 0.3

Δ T = 0.5

Δ T = 1

Δ T = 5

Figure 6.5: Spatial distribution of small particles at various times due to hindered diﬀusion. All

particles are located at Z

= 2 at T = 0.

0 5 10 15

0

0.05

0.1

0.15

0.2

0.25

Z’

P

D

F

Δ T = 0

Δ T = 0.0001

Δ T = 0.001

Δ T = 0.01

Δ T = 0.1

Δ T = 1

Δ T = 10

Figure 6.6: Spatial distribution of particles located within the range of 1 < Z

< 5 at T = 0. The

distributions are taken after various inter-acquisition times, ∆T.

60

0 2 4 6 8 10

30

40

50

60

70

80

90

100

Δ T

%

R

e

m

a

i

n

i

n

g

i

n

I

m

a

g

i

n

g

R

a

n

g

e 1.0 < Z

0

< 3.0

1.0 < Z

0

< 5.0

3.0 < Z

0

< 5.0

Figure 6.7: Percentage of particles in the imaging range for diﬀerent inter-acquisition time. The

imaging range is the same as the initial particle distribution range, Z

0

.

in measurements.

As mentioned previously, the major concern for PIV is the percentage of particle drop-in’s and

drop-out’s because all imageable particles at the time of image acquisition are analyzed without

any eﬀort to distinguish the entering and the leaving. The percentage of particles that do not

drop out for various inter-acquisition time is shown in 6.7, which is in agreement with a separate

numerical study conducted by Sadr et al. [59] Not surprisingly, a longer times between consecutive

acquisition results in a lower percentage of “good” particles, which are particles that do not drop

out. In dimensional terms, more than 90% of 100-nm particles remain in the imaging range of

100 < z < 300 nm (10% drop-out) if image acquisitions are taken at 1 msec apart. However, this

percentage drops to 65% if the inter-acquisition time is 10 msec. Based on this result, near-wall PIV

measurement with sub-micron particles should be conducted with a inter-acquisition time as short

as possible to ensure accuracy. If an acceptable percentage of drop-out’s is 95%, the acquisitions

should be taken with ∆T < 0.2, or ∆t = 0.5 msec for 100-nm radius tracer particles. The drop-

out’s, however, present less of a problem for Particle Tracking Velocimetry (PTV) as the technique

makes an eﬀort to distinguish the particle drop-in’s and drop-out’s.

6.3.4 Horizontal Apparent Velocity Distributions

Subsequent analysis concentrates on horizontal motion of particles that do not drop out, emulating

physical TIRV measurements. In particular, the focus is on the eﬀect of shear on apparent velocity

measurements. Shown in ﬁgure 6.8 is the distribution of non-dimensional apparent velocity, V =

∆X

**/∆T, for particles under various Peclet number, Pe, or equivalently the shear rates. It is
**

clearly observable that the apparent velocity PDF’s widen and skew as shear rate increases. This

agrees well with experimentally measured PDF’s reported by Jin et al. [80] and Huang et al. [85].

Jin et al. suggested that the increasing skewness and widening of the apparent velocity distribution

61

0 10 20 30 40 50

0

0.2

0.4

0.6

0.8

V

P

D

F

Pe = 0.5

Pe = 1

Pe = 3

Pe = 5

Pe = 10

Figure 6.8: Apparent velocity distribution of particles remaining in the imaging range 1 < Z < 3

after ∆T = 10. Larger Pe leads to an apparent velocity distribution with larger mean, width, and

skewness.

−3 −2 −1 0 1 2 3

0

0.5

1

1.5

(V−V

avg

)/V

avg

P

D

F

Pe = 0.3

Pe = 0.5

Pe = 1

Pe = 3

Pe = 5

Pe = 10

Pe = 30

Figure 6.9: Normalized apparent velocity distribution of particles remaining in the imaging range

1 < Z < 3 after ∆T = 10. V

avg

is the mean of each apparent velocity PDF. The normalized

PDF’s collapse onto each other at Pe > 3. In general, larger Pe has a narrower but more skewed

normalized PDF.

62

0 50 100 150

0

0.01

0.02

0.03

0.04

0.05

V

P

D

F

1 < Z

0

< 2

2 < Z

0

< 3

3 < Z

0

< 4

4 < Z

0

< 5

5 < Z

0

< 6

Figure 6.10: Apparent velocity distribution of particles at various imaging ranges. All apparent

velocity distributions are measured at ∆T = 10 and Pe = 10. Particles that start oﬀ farther away

from the surface move faster because they are carried by ﬂuids at higher velocity planes, and their

distributions are more symmetric due to less inﬂuence of the wall and hindered diﬀusion.

violates the symmetric PDF assumption of PIV analysis and could lead to measurement errors.

Upon further analysis, it is observed that the apparent velocity PDF’s can collapse onto a single

distribution for Pe > 3, as shown in ﬁgure 6.9. It is noted that the collapsed PDF’s for Pe > 3

have a smaller distribution width but a larger skewness, while the distributions of Pe < 3 are wider

but more symmetric. The explanation is that at low shear rates, the horizontal displacement of

the particle ensemble is dominated by diﬀusion, leading to a wider normalized PDF. At high shear

rates, on the other hand, the ﬁnite thickness of the imaging range and shear eﬀect give rise to

the skewness and distribution widening. This physical explanation is supported by the fact that

both skewness and distribution width are scalable by the shear rate only at Pe > 3. The same

shear-dominance eﬀect at Pe > 3 has been reported experimentally by Huang et al. [85], and the

agreement of BD simulations further validates the presented conclusion.

Another source of apparent velocity distribution skewness is the hindered diﬀusion and the

presence of the wall. One can observe in ﬁgure 6.10 that the apparent velocity PDF’s of imaging

ranges farther away from the wall are wider and less skewed than that of imaging ranges closer to

the wall. The diﬀerence is even more obvious if each PDF is re-scaled by its distribution mean,

V

avg

, as plotted in ﬁgure 6.11. The combined eﬀect of the hindered diﬀusion and the shear-induced

rotational slow-down in the near-wall region causes the apparent velocity PDF’s to skew, while at

far away the wall presence is not felt and the symmetric distributions again show scaling similarity.

6.3.5 Time Evolution of Apparent Velocity Distributions

Finally, the time evolution of apparent velocity distributions was examined and shown in ﬁgure

6.12. For a ﬁxed Pe, it is observed that diﬀusion is quite dominant at small ∆T, leading to apparent

63

−100 −50 0 50 100

0

0.01

0.02

0.03

0.04

0.05

V − V

avg

P

D

F

1 < Z

0

< 2

2 < Z

0

< 3

3 < Z

0

< 4

4 < Z

0

< 5

5 < Z

0

< 6

6 < Z

0

< 7

7 < Z

0

< 8

Figure 6.11: Collapsed apparent velocity distribution shown in ﬁgure 6.10. The PDF’s are scaled

by subtracting their corresponding distribution mean, V

avg

.

−300 −200 −100 0 100 200 300 400

0

0.005

0.01

0.015

0.02

0.025

V

P

D

F

Δ T = 0.0001

Δ T = 0.01

Δ T = 0.01

Δ T = 0.1

Δ T = 1

Δ T = 10

Figure 6.12: Time evolution of apparent velocity distribution. All apparent velocity PDF’s are

obtained at Pe = 30 and with particles within the imaging range of 1 < Z

< 3 at T = 0. Note

that the apparent velocity distribution narrows and skews with increasing inter-acquisition time,

∆T.

64

0 2 4 6 8 10

0.9

0.95

1

1.05

1.1

1.15

Δ T

V

a

v

g

/

V

s

h

e

a

r

Pe = 0.3

Pe = 0.5

Pe = 1

Pe = 3

Pe = 5

Pe = 10

Pe = 30

Figure 6.13: Time evolution of mean particle apparent velocity. Each data point represents the

mean value of one apparent velocity distribution shown in ﬁgure 6.12. All mean apparent velocities

are obtained from particles that remained at imaging range of 1 < Z < 3. V

shear

is the calcu-

lated velocity of the particles in a near-wall shear ﬂow if there is no Brownian motion, and is the

target quantity that velocimetry is trying to measure. Thus V

avg

/V

shear

can be interpreted as the

accuracy of velocimetry measurement. Note that data of all Pe show a minimum velocity ratio at

approximately ∆T = 1.

65

10

−3

10

−2

10

−1

10

0

10

1

0.9

1

1.1

1.2

1.3

1.4

1.5

ΔT/W

2

V

a

v

g

/

V

s

h

e

a

r

W = 2

W = 4

W = 6

W = 8

W = 10

Figure 6.14: Rescaled time evolution of mean particle apparent velocity. For each data series, the

imaging range is set at 1 < Z

**< W and the non-dimensional time is rescaled with 1/W
**

2

. Note that

the velocity ratios, V

avg

/V

shear

, collapse onto each other under this rescaled time scheme, except

near the minimum. Minimal velocity ratios for all W’s occur near an alternative non-dimensional

time scale of ∆T/W

2

≈ 10

−1

. All data series have Pe = 30.

velocity distributions that are signiﬁcantly wider than that of at large ∆T. Due to increased shear

dominance, the apparent velocity distribution narrows as time increases. Such change can be

explained by the fact diﬀusive velocity distribution wideth scales with ∆T

−1/2

,

¸∆X) ∼

√

∆T ⇒ ¸V ) =

¸∆X)

∆T

∼

1

√

∆T

, (6.12)

while the shear-induced ﬂow velocity distribution width scales linearly with ∆T. Thus diﬀusion

accounts for a large fraction of the measured apparent velocity at short inter-acquisition time,

while the majority of the measure velocity is due to the shear ﬂow at large ∆T. This explains

the narrowing of the apparent velocity distributions in ﬁgure 6.12 as ∆T increases. Clearly, if the

apparent velocity distributions evolve with time, it would be of interest to see if the mean value of

the velocity distributions evolve as a function of time as well.

The goal of vecimetry measurements is to accurately estimate ﬂuid velocities using the tracer

particle apparent velocity as an estimator. If V

shear

is deﬁned as the mean velocity of all ﬂuidic

planes inside the imaging range and V

avg

is the mean value of an apparent velocity distribution such

as the ones shown in ﬁgure 6.12, then V

avg

/V

shear

can be interpreted as velocimetry measurement

accuracy with V

avg

/V

shear

= 1 being the ideal measurement. The time dependence of the velocity

ratio V

avg

/V

shear

is shown in ﬁgure 6.13. It can be observed that all V

avg

/V

shear

ratios exhibit the

form of a concave-up function of ∆T, with a minimum occurring at approximately ∆T = 1. The

velocity ratio would keep increasing as ∆T increases. Figures 6.12 and 6.13 demonstrate that both

the shape and the mean of an apparent velocity distribution are not time-invariant.

With further analysis, it can be observed that the values of ∆T at which the minima of

V

avg

/V

shear

ratio occur depend on the thickness of the imaging range. In their paper Sadr et al. [59]

suggested an alternative time scale, ∆T/W

2

, if the imaging range is deﬁned at 1 < Z

< W. This

alternative time scale, therefore, can be interpreted as the time it takes for a particle in contact

66

path 2

path 1

Imaging

range

Figure 6.15: Schematic of 2 potential paths for particle translation. Between image acquisitions,

particles that have taken diﬀerent paths could have travelled diﬀerent distances while sampling

diﬀerent velocities along the way. Two potential paths of a particle are shown in this ﬁgure. If

the particle takes path 1, it samples the velocities of the lower planes and thus translates a short

horizontal distance. On the other hand if the particle takes path 2, it samples the higher velocities

of planes that are out of the imaging range, and thus translates a larger horizontal distance.

with the wall to diﬀuse out of imaging range due to Brownian motion. Using this non-dimensional

time scale, ﬁgure 6.14 demonstrates that the velocity ratio V

avg

/V

shear

also has a scaling similarity.

In addition, it should be noted that in both ﬁgures 6.9 and 6.14, V

avg

/V

shear

→ 0 at ∆T → 0 as

the instantaneous apparent velocities of particles would be the closest to the local ﬂuidic velocities.

So why is the velocity ratio minimal at ∆T/W

2

≈ 10

−1

, and increases monotonically afterward?

The answer to this question lies in ﬁgure 6.5 and is illustrated in ﬁgure 6.15. For small ∆T, the

skewed distribution of particles toward the wall suggests that the imaged particles are more likely

to move closer to the wall. That is, path 1 in ﬁgure 6.15 is more likely to be taken than path

2. Since drop-out’s are less signiﬁcant for small ∆T, the consequence is that the tracer particles

sample toward the lower velocity planes, and thus the mean apparent velocity decreases. On the

other hand for large ∆T, some of the particles that have left the imaging range are given enough

time to return at the second acquisition, such path 2 illustrated in ﬁgure 6.15. The larger the ∆T,

the higher probability that particles can sample farther away from the surface and still manage to

return to the imaging range at the time of second image acquisition. Because they have sampled

the ﬂuidic velocities of the higher shear planes, these contributions of ﬂuidic velocities outside of

the imaging range are reﬂected in the higher values of mean particle apparent velocities.

Clearly, the physical reasoning described in the previous paragraph suggests that the thickness of

the imaging range would be an important parameter, which justiﬁes the scaling of non-dimensional

time ∆T with 1/W

2

. Indeed Sadr et al. used the Fokker-Planck approach to study the PDF

of ﬂuidic planes that an ensemble of particles would have sampled between image acquisitions in

nano-PIV. They obtained a ratio of averaged Z

**value sampled by the particles to the mid-distance
**

of the imaging range, (W + 1) /2. The time dependence of this ratio is in striking resemblance to

that shown in ﬁgure 6.14. In both cases, the turning point in the relative contribution of the two

groups of particles (the ones that move closer to the surface and the ones that sample the higher

shear plane and return) occurs at ∆T/W

2

≈ 10

−1

. This suggests that the percentage of particle

drop-out and the positions whose ﬂuidic velocities are sampled by the particles play a crucial role

in the accuracy of velocimetry measurements.

Figures 6.13 and 6.14 can also serve as guides for choosing the appropriate ∆T for near-wall

particle tracking velocimetry. First, one can observe in ﬁgure 6.13 that the velocity ratio is Pe-

67

invariant except near the minimum where ﬂuctuations exist. Thus the selection of ∆T such that

the velocity ratio would be minimum should be avoided. Such avoidance is further reinforced by the

observation that the velocity ratio in ﬁgure 6.14 is not W-invariant in regions near the minimum.

It can be clearly observed that the “dip” in velocity ratio depends on the values of W, where large

W values lead to a lower minimal velocity ratios, while the velocity ratio shows no dependence on

W at both the higher and lower ends of the time scale ∆T/W

2

. These observations suggest that

choosing an inter-acquisition time of ∆T/W

2

∼ O

_

10

−1

_

would most likely yield measurement

inaccuracy.

6.4 CONCLUDING REMARKS

Brownian dynamics simulation oﬀers an attractive approach to the study of near-wall particle dy-

namics. We demonstrate that wall-induced hindered diﬀusion and translational slow-down of a

colloidal particle in a simple shear ﬂow can be accurately captured by Brownian dynamics sim-

ulations, with results conﬁrmed by experimental data. In near-wall colloidal dynamics, physical

length and time scales are particle radius and diﬀusive time, and the problem can be mathematically

closed by specifying a Peclet number and a sedimentation constant. In the direction perpendic-

ular to the wall, hindered diﬀusion skews the displacement distributions toward to wall. In the

direction parallel to the wall, colloidal particle motion is dominated by shear when Peclet number

is greater than 3, with hindered diﬀusion also contributing to changes in the velocity distribution

width and its skewness. Furthermore, velocity distributions evolve as a function of time, reporting

mean velocities that are time-dependent with a minimum at ∆T/W

2

≈ 10

−1

.

This study also provides an assessment tool to the relative accuracy of near-wall PIV and PTV.

Because of a large amount of drop-in’s and drop-outs when nanoparticles are used, the inaccuracy

of PIV in near-wall measurement could be signiﬁcant. PIV will remain accurate as long as the

time between acquisition is much smaller than the diﬀusion time of tracer particles. As tracer

particles get smaller and their diﬀusion become greater, the incapability of imaging equipments to

make consecutive image acquisitions with an extremely short inter-acquisition time would limit the

applicability of PIV in near-wall measurements.

On the other hand, PTV and SPTV (Statistical Particle Tracking Velocimetry) [94] are much

more reliable measurements because PTV attempts to exclude particle drop-in’s and drop-out’s

while SPTV treats the drop-in’s and drop-out’s as statistical noise. The potential error of both

methods would stem from biased sampling of the velocities at various shear planes. However, ﬁgure

6.14 oﬀers a way to correct for this bias. By using it as a scaling guide, the correct shear-induced

velocity of the particles can be retrieved from the measured mean velocity values. An alternative

method is to calculate which inter-acquisition time would result in the measured mean velocity

being equal to the shear-induced velocity before experiments are conducted. Neither correction

method can be applied to PIV measurements.

Chapter 7

Concluding Remarks and Suggested

Studies

In this dissertation we have presented our experimental studies of aqueous solution boundary slip

and anisotropic hindered diﬀusion, and described the total internal reﬂection velocimetry (TIRV)

method used in these experiments. A Brownian dynamics simulation study is also presented to

compare the eﬀectiveness and accuracy of TIRV and nano-PIV. Furthermore, these studies open

up opportunities for future experimental works in the areas of ﬂuid mechanics and colloidal science.

First of all in pursuing a better understanding of boundary slip, water is by no means the

only test ﬂuid of interest. Water and similar solvents such as alcohols have a polar molecular

conﬁguration, and their chemical properties are vastly diﬀerent from the non-polar group of solvents,

such as hexane and toluene. It would certainly be of scientiﬁc interest to see if the solvent molecular

polarity would have an eﬀect on boundary slip, and if the solid surface charges would interact with

the weak charges carried by the solve molecules.

The TIRV technique can certainly be extended to near-surface measurements in a gas phase.

Although the existence of boundary slip at a gas/solid interface has been well documented, the

TIRV technique oﬀers a method to make direct measurement of the gas slip velocities. In addition,

TIRV can also be applied to experimentally investigate ﬂow characteristics within the gas boundary

layer. Of course, ﬂuorescent aerosols would be required as tracer particles, and we believe such

technology is possible in the near future.

Returning to the liquid phase, particle or cell adhesion and desorption are both areas of great

interests in colloidal science and biology, and the TIRV technique is ideal for studying these phe-

nomena. The area of interest include both speciﬁc and non-speciﬁc binding of suspensions and

the solid boundary. To investigate speciﬁc chemical binding, the particles and the solid boundary

surface can be coated with molecules that bind correspondingly, such as ligands and receptors to

study blood cell adhesion. Besides binding, kinetics of surface-based chemical reactions can also be

studied with the same mechanism.

Understandably, advancement of technology would soon deem particles of 100 nanometer in-

suﬃcient in probing the near-wall region as scientists would like to look even closer to the solid

surface. Thus a new breed of tracer particles or molecules in the order of 1 nanometer would be

needed. In fact, quantum dots have been viewed as the next generation of tracer probes, and their

usage under evanescent wave imaging settings have been demonstrated by Pouya et al. [100] and

Guasto et al. [94]. These quantum dots are small (a few nanometer in diameter), more uniform in

size than polystyrene ﬂuorescent particles, and available in water or organic solvent soluble forms,

thus making them an ideal candidate to probe regions that are even closer to the wall with a variety

68

69

of liquids. Perhaps a more accurate measurement of the slip velocities can be achieved by using

quantum dots in TIRV.

The Brownian motion of these quantum dots is undoubtedly much more signiﬁcant and the par-

ticle tracking method in the TIRV will be incapable of dealing with the large proportion of particle

drop-in’s and drop-out’s between image acquisitions. An additional limitation of the particle-

tracking based TIRV is its requirement of low particle seeding density to avoid tracking ambiguity.

In some experimental situations, however, a high seeding density might be desirable to preserve

the particle-particle interactions and/or to increase measurement eﬃciency. The statistical particle

tracking velocimetry (SPTV) developed by Guasto et al. [94] is a perfect solution to these prob-

lems. They proposed that the true statistics of the desired physical displacement can be extracted

by matching each detected particle to all others, provided that experimental parameters such as

camera noise, imaging depth, particle size and diﬀusivity, and seeding density are known. The

SPTV thus eliminates the needs to keep track of particle drop-in’s and drop-out’s and to unam-

biguously matching detected particles. It is certainly more advantageous than other particle-based

velocimetries, especially in near-surface measurements.

Appendix A

Calibration of beam incident angle

In our TIRV setup, the total internal reﬂection was created at the glass/water interface by directing

a laser beam through a microscope objective lens. Knowing the beam incident angle is critical in

determining evanescent ﬁeld penetration depth. In this appendix, the measurement method of the

illumination beam incident angle is presented.

As demonstrated in equation (2.3), it would be ideal if one can measure the beam incident angle

directly when determining the penetration depth. In practice, because the total internal reﬂection

bends the reﬂected beam back into the objective lens, as shown in ﬁgure 2.1, such measurement is

extremely diﬃcult.

The illumination laser beam is directed into the objective lens by passing through the a con-

verging lens. The bending of the beam is achieved by translating the converging lens [47]. Thus

a geometric relation should exist between the the lens translation distance and the beam incident

angle, and this relation should be true for all incident angles despite of total internal reﬂection. To

determine this relation, the laser beam is directed through the objective as used in a non-TIRF

setup. The beam is then allowed to refract at a glass/air interface, as shown in ﬁgure A.1. Snell’s

law determines the refraction angle by

n

1

sin φ = n

2

sin θ, (A.1)

where n

1

and n

2

are refractive indices of glass and air, respectively. The refracted beam in air is

then projected to a far-away wall or ceiling where the refractive angle can be measured accurately

(shown in ﬁgure A.2).

By examining the data, we found a linear relationship between the lens position, x, and sin θ.

Using equation (A.1), an empirical linear relation between x and sin φ was found (shown in ﬁgure

A.3). The best ﬁt line was then extended to φ greater than critical angle to determine incident

angle. The empirical equation was found to accurately predict the lens position of critical angle.

70

71

Glass

Air

φ

θ

Figure A.1: Schematic of laser beam refraction at the glass/air interface.

θ

Figure A.2: Photo and schematic of beam incident angle measurement. The refraction angle θ is

the same as that of ﬁgure A.1.

72

8.5 9 9.5 10 10.5 11

−0.2

0

0.2

0.4

0.6

0.8

x (mm)

s

i

n

(

φ

)

sin(φ) = − 0.33 x + 3.5

Data

Linear fit

Figure A.3: Plot of laser beam angle vs. converging lens position.

Appendix B

Shear-induced lift force (or more

precisely, lack of ) on near-wall

submicron-particles

It has been suggested that a shear-induced lift force can act on suspended particles in a linear

shear ﬂow, making them more likely to move away from a solid boundary. This would result in a

non-uniform distribution of particles near our glass solid surface, where our total internal reﬂection

velocimetry (TIRV) measurements take place. Because our statistical analysis is based on the

assumption of uniform particle distribution, the shear-induced lift force would lead to signiﬁcant

inaccuracies. However, we believe that such a lift force is insigniﬁcant in our ﬂow regime, and in

this appendix, an established theory is presented to support our argument.

The subject of lift forces acting on a small sphere in a wall-bounded linear shear ﬂow has been

thoroughly studied by Cherukat & McLaughlin [87]. Here we will present only the theory that

applies to the ﬂow conditions under consideration. Suppose that a free-rotating rigid sphere of

radius a is in a Newtonian incompressible ﬂuid of kinematic viscosity ν and is in the vicinity of a

solid wall. In the presence of a linear shear ﬂow, the free-rotating sphere can can travel at a velocity

U

sph

that is diﬀerent from the ﬂuid velocity, U

G

, of the shear plane located at its center [38]. We

can deﬁne a characteristic Reynolds number based on the velocity diﬀerence, U

s

= U

sph

−U

G

, with

Re

s

=

U

s

a

ν

. (B.1)

Another characteristic Reynolds number based on shear rate can be deﬁned as

Re

G

=

Ga

2

ν

, (B.2)

where G is the wall shear rate. In this geometry, the wall can be considered as located in the ”inner

region” of ﬂow around the particle if Re

s

¸κ and Re

G

¸κ

2

, where κ ≡ a/h and h is the distance

between the particle’s center and the wall. For near-wall particle velocimetry described in chapters

3 and 4, Re

s

∼ Re

G

∼ 10

−7

while κ ∼ O(1), and thus the inner region theory of lift force applies.

For a ﬂat wall located in the inner region of ﬂow around a free-rotating particle, the lift force,

F

L

, which is perpendicular to the wall, is scaled by [87]

F

L

∼ Re

s

I, (B.3)

73

74

where I is a coeﬃcient that can be numerically estimated by

I =

_

1.7631 + 0.3561κ −1.1837κ

2

+ 0.845163κ

3

¸

−

_

3.21439

κ

+ 2.6760 + 0.8248κ −0.4616κ

2

_ _

Re

G

Re

s

_

+

_

1.8081 + 0.879585κ −1.9009κ

2

+ 0.98149κ

3

¸

_

Re

G

Re

s

_

2

.

(B.4)

Again for the velocimetry conditions described in chapters 3 and 4, I ∼ O

_

10

2

_

. Therefore

F

L

∼ Re

s

I

_

10

−7

_ _

10

2

_

¸1, (B.5)

and the lift force acting on near-wall particles is insigniﬁcant and can be neglected for all practical

purposes.

Appendix C

Evanescent wave image of

micron-sized ﬂuorescent particles

Imaging of ﬂuorescent nanoparticles under TIRFM have been well reported by many groups, partic-

ularly in the exponential decay relation between particle intensity and its distance to the substrate

surface [44, 85, 90]. But for micron-sized ﬂuorescent particles in evanescent ﬁeld, there has been no

report on their imaging characteristics. In this appendix, numerical simulations were performed to

investigate some of the imaging characteristics associated with ﬂuorescent particles under evanes-

cent wave imaging.

The numerical simulation was conducted in the commercially packaged COMSOL Multiphysics

software environment. The simulation geometry is simpliﬁed from three-dimensional to two-

dimensional but is still a representative of near-surface imaging, and shown in ﬁgure C.1. Polystyrene

particles (refractive index 1.59) of three diﬀerent diameters, d/λ = 0.39, 6 and 12 where λ is the

incident beam wavelength, are immersed in the water phase (refractive index 1.33) and placed in

the vicinity of the glass phase (refractive index 1.51). A Gaussian beam enters from the lower-left

boundary and reﬂects oﬀ the water/glass interface at a 64.54

◦

angle, while scattering boundary

conditions are applied to all other external boundaries. Simulations were repeated for various gap

sizes, h, between the particle and the glass, with h/λ ranging from 0 to 2. The eﬀectiveness of the

COMSOL Multiphysics package in modelling total internal reﬂection and evanescent ﬁeld was ﬁrst

demonstrated in the absence of a polystyrene particle, and is shown in ﬁgure C.2. The simulation

model perfectly captures total internal reﬂection and an exponential decay of evanescent energy

density in the water phase is found to be in agreement with theories (shown in ﬁgure C.3).

Time-averaged energy densities of particles in evanescent ﬁeld are shown in ﬁgures C.4, C.5 and

C.6, respectively. In ﬁgure C.4, it can be observed that the presence of a particle with diameter

d/λ = 0.39 does not distort the energy ﬁeld. In contrast, larger particles such as d/λ = 6 and

12 can distort the energy ﬁeld quite signiﬁcantly. Their presence can be seen to create a shadow

in the reﬂected beam. These lost energy leaks into the interior of the large particles through

a “frustrated-total internal reﬂection mechanism”, illuminating regions beyond the penetration

depth of evanescent wave. These energy continue to reﬂect and refract at the polystyrene/water

interface, resulting in a high energy density in the lower-right side of the particle, while some

additional energy escapes into the right half of the water phase.

Using the subdomain integration function of COMSOL, one can ﬁnd out the overall energies

inside the polystyrene particles. This quantity is important because in TIRFM experiments, only

the light emitted by the ﬂuorophores inside the polystyrene particles is imageable, and the ﬂuo-

rophores are excited only by the light energy that enters the particles. The overall energies that

75

76

Incident Gaussian Beam

Glass Phase

Water Phase

Polystyrene Particle

Figure C.1: Schematic of COMSOL simulation geometry. A polystyrene particle is suspended

in the water phase and located in the vicinity of glass’interface. Scattering (or ﬂoating) boundary

condition is applied to all external boundaries at the water and glass phases, except at the boundary

inside the glass phase where the incident Gaussian beam enters. Because the incident angle of the

Gaussian beam is 64.54

◦

, a total internal reﬂection occurs at the glass/water interface. The particle

shown in the ﬁgure has a diameter of d/λ = 6.

Figure C.2: COMSOL simulation of total internal reﬂection. Plotted in the ﬁgure is time-averaged

total energy density of total internal reﬂection at a glass/water interface. The geometry of this

simulation is identical to that of ﬁgure C.1, except the presence of a suspended particle.

77

0 0.5 1 1.5 2

0

0.2

0.4

0.6

0.8

1

h/λ

N

o

r

m

a

l

i

z

e

d

I

n

t

e

n

s

i

t

y

Simulation

Theory

Figure C.3: The exponential intensity decay of evanescent ﬁeld in ﬁgure C.2. Close agreement

between simulation results and theoretical calculations is obtained.

Particle

Figure C.4: COMSOL simulation of a particle with d/λ = 0.39 in evanescent ﬁeld. Plotted in the

ﬁgure is time-averaged total energy density, and the geometry of this simulation is identical to that

of ﬁgure C.1, except that the particle diameter is with d/λ = 0.39 and the gap size between the

particle and the glass surface is h/λ = 0.1.

78

Figure C.5: COMSOL simulation of a particle with d/λ = 6 in evanescent ﬁeld. Plotted in the

ﬁgure is time-averaged total energy density, and the geometry of this simulation is identical to that

of ﬁgure C.1, except that the gap size between the particle and the glass surface is h/λ = 0.1.

Figure C.6: COMSOL simulation of a particle with d/λ = 12 in evanescent ﬁeld. Plotted in the

ﬁgure is time-averaged total energy density, and the geometry of this simulation is identical to that

of ﬁgure C.1, except that the particle diameter is d/λ = 12 and the gap size between the particle

and the glass surface is h/λ = 0.1.

79

0 0.5 1 1.5 2

0

0.2

0.4

0.6

0.8

1

h/λ

N

o

r

m

a

l

i

z

e

d

I

n

t

e

n

s

i

t

y

d/λ = 0.39

d/λ = 6

d/λ = 12

Evanescent Field

Figure C.7: Overall evanescent energy in the suspended particles at various gap sizes. The in-

tensities are normalized by the intensity observed when the particle is in contact with the glass

surface. The evanescent ﬁeld intensity is obtained from the cross-sectional time-averaged total

energy density proﬁle of ﬁgure C.2.

enter the particles at gap sizes h/λ ranging from 0 to 2 is shown in ﬁgure C.7. As it has been

demonstrated by Huang et al. [85] and Sarkar et al. [90], the overall intensity of a small particle

(d/λ = 0.39) follows an exponential decay function that is identical to the evanescent energy decay.

This forms the basis of using the overall intensity of nanoparticles for 3D displacement tracking.

The overall intensity of larger particles, however, does not follow the same exponential decay func-

tion of the evanescent ﬁeld, particularly at small gap sizes. This is probably due to the fact that

a larger radius of curvature provides more surface area for light to leak into the particles through

the frustrated-total internal reﬂection mechanism. Still, a near-exponential dependency of large

particle intensity on the gap size is observed in ﬁgure C.7.

A more relative question is what will a ﬂuorescent particle with diameter greater than the

illumination wavelength look like under a high numerical aperture (NA), high magnitude objective

whose focal depth, δ, is roughly δ/λ = 2. One of the ways to ﬁnd out is to convolute the energy

density inside the particles with diﬀraction equation and point spread function. However, such a

convolution is computationally complicated and expensive. A simpler way is to look at the intensity

proﬁle when the ﬂuorescent energy is projected onto the focal plane, with which one could still gain

some qualitative understanding of the image. For a point light source that is a distance z oﬀ the

focal plane, it’s intensity is [101]

I (z) =

_

sin (u/4)

u/4

_

2

I

0

(C.1)

where I

0

is the point source emission intensity and

u =

2π

λ

_

a

f

_

2

z. (C.2)

Here λ is the wavelength, a is the radius of the objective lens and f is the objective focal length. In

80

−4 −2 0 2 4

0

0.2

0.4

0.6

0.8

1

I

/

I

0

x/λ

Figure C.8: Cross-sectional intensity proﬁle of a 3-µm particle (d/λ = 6). The blue squares

represent the cross-section intensity proﬁle indicated as a red line in ﬁgure C.9. The red dotted

line, however, represents the projected intensity proﬁle based on results of COMSOL simulation of

a particle of the same size and equation (C.3). I

0

is the peak intensity and x/λ = 0 corresponds to

the particle geometric center. The direction of the evanescent wave propagation is toward positive

x/λ.

getting equation (C.1), it is assumed that both a and f are much larger than λ. a/f is commonly

referred to as the f-number of lens and for a microscope objective, it is equal to the numerical

aperture [73]. Therefore, for a particle in contact of the wall and its center is located at x = 0 and

z = a, its projected intensity at point x = x

0

on the z = z

0

plane is [101]

I

p

(x

o

) =

_

2a−b

b

I (x

0

, z) zdz (C.3)

where b = a−

_

a

2

−x

2

0

and I (x

0

, z) is calculated using equation (C.1). This projection is obviously

a simpliﬁed calculation as it assumes negligible diﬀraction. This leads to physical inaccuracy as we

will demonstrate subsequently.

The intensity projection of a particle with d/λ = 6 is shown in ﬁgure C.8 as a red dotted line,

where the focal plane is set at the glass surface. In the projection, the intensity exhibits a peak value

near the particle center, while a longer tail is observed in the direction of the laser beam propagation.

A TIRFM image of a 3-µm particle (equivalently d/λ = 6) is shown in ﬁgure C.9. A peak intensity

near the center can be clearly observed in the image. For comparison, a cross-sectional intensity

proﬁle of ﬁgure C.9 is also shown in ﬁgure C.8 as blue squares. This intensity proﬁle is similar in

shape when compared to that of red dotted line from simulation. A peak intensity is found near the

particle center, while a slightly longer tail is found in the direction of evanescent wave propagation.

However, the intensity proﬁle from actual imaging of a particle appears to be wider than that of the

simulated result. This is due to the fact that the computation leading to the projection (red dotted

line) in ﬁgure C.8 neglects diﬀraction of light, which is important in microscopy. Nevertheless, the

81

1 µm

Figure C.9: Digital image of a 3-µm particle (d/λ = 6) in contact with glass surface. The intensity

proﬁle along the red cross-section shown is plotted in ﬁgure C.8.

resemblance of of the two proﬁles is striking and the proﬁles are in qualitative agreement.

The same imaging projection is also performed for a 6-µm particle (d/λ = 12) and shown in

ﬁgure C.10. With a particle of this size, we can again see that there is a bright peak near its center,

while the asymmetric tail on the right side is even more pronounced. A similar observation can be

made on an actual image of a 6-µm particle (ﬁgure C.11) as well as on a cross-sectional intensity

proﬁle (ﬁgure C.10, blue squares). A large bright center is clearly visible while the right half of

the particle is signiﬁcantly brighter. In addition, toward the right tip, there are small, alternating

regions of bright spots, which can be also be observed in the right tail of the red simulation intensity

proﬁle in ﬁgure C.10. Again, the modelling results and the actual image show qualitative agreement

despite the simplicity of the integration model in equations (C.1) and (C.3). However, as observed in

ﬁgure C.8, the intensity proﬁle obtained from the simulation results and equation (C.3) is narrower

than that of an actual image because of the neglected diﬀraction in numerical integration.

82

−6 −4 −2 0 2 4 6

0

0.2

0.4

0.6

0.8

1

x/λ

I

/

I

0

Figure C.10: Cross-sectional intensity proﬁle of a 6-µm particle (d/λ = 12). The blue squares

represent the cross-section intensity proﬁle indicated as a red line in ﬁgure C.11. The red line,

however, represents the projected intensity proﬁle based on results of COMSOL simulation of a

particle of the same size and equation (C.3). I

0

is the peak intensity and x/λ = 0 corresponds to

the particle geometric center. The direction of the evanescent wave propagation is toward positive

x/λ.

2 µm

Figure C.11: Digital image of a 6-µm particle (d/λ = 12) in contact with glass surface. The

intensity proﬁle along the red cross-section shown is plotted in ﬁgure C.10.

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This report is the PhD thesis of Peter Huang, supervised by Prof. Kenneth Breuer in the Division of Engineering, and submitted to the Graduate School at Brown University in September 2006. For more information contact: kbreuer@brown.edu

i

Abstract Aqueous boundary solution slip at a solid surface and hindered diﬀusion of suspended nearsurface particles are experimentally investigated with a three-dimensional total internal reﬂection velocimetry (3D-TIRV) technique. The sub-micrometer penetration depth of evanescent wave oﬀers low-background-noise images where a 10-nm displacement can be accurately measured. At shear rates less than 1800 sec−1 , a shear-induced slip length of less than 100 nanometers is observed at a glass surface of sub-nanometer roughness. Surface hydrophobicity is also found to aid slip. However, the notion that electrokinetic and electrostatic forces acting on charged tracer particles lead to slip length measurement inaccuracy is disputed by experiments conducted with aqueous solutions consisting of electrolytes, which report slip length of similar magnitudes. Anisotropic hindered diﬀusion of suspended near-surface particles is demonstrated with simultaneous threedimensional measurements. Hindered diﬀusion coeﬃcients of 1.5-µm radius particles within 300 nm from the solid wall are shown to be in close agreement with previously published theories. Lastly, eﬀects of hindered diﬀusion and wall presence on the accuracies of TIRV and other nearsurface measurement methods are studied via Brownian dynamics simulations. The results reveal that hindered diﬀusion causes a minor bias toward values obtained at the wall if a small interval is allowed between successive image acquisitions, while particle drop-outs lead to over-estimation of ﬂuidic velocity values if the time interval between image acquisitions is large. It is also found that the apparent velocities of near-wall particles are not time-invariant. Still, true ﬂuidic velocity values can be obtained from the particle apparent velocities with proper scaling. Such scaling correction is applicable to particle tracking velocimetry measurements, but not to correlation based velocimetry measurements for their lack of accounting of particle drop-outs. Shear eﬀect on near-wall particle translation in a ﬁnite imaging depth results in an asymmetric apparent velocity distribution, which is another potential source of error for correlation based velocimetries. These ﬁndings lead to a conclusion that particle tracking based velocimetry methods, such as TIRV, are more superior than correlation based velocimetry methods are in making near-surface ﬂuidic measurements.

Copyright. c . 2006 i . Pong-Yu (Peter) Huang.

He currently resides in the New England region with his wife and plans to pursue an academic career. Taiwan and attended schools there until the age of ﬁfteen. and continued to pursue a Doctor of Philosophy degree since 2003. After graduating high school from International School Manila in 1996. ii . he attended Cornell University where he received a Bachelor of Arts degree in physics in 2000. Huang enjoys travelling and anything related to baseball (except sabermetrics). he completed a Master of Science degree in engineering. In 2002. Upon graduation. and holds great interests in economic perspectives of events in the world. He is a proud fan of the New York Mets since 1999.Pong-Yu (Peter) Huang was born in Taipei. he enrolled at the Division of Engineering. Brown University. Mr. to pursue a graduate degree under the guidance of Professor Kenneth Breuer.

pp. 37. 2006. To be submitted to Physical Review E. Guasto and Kenneth S. Included are an overall review and summary of the whole dissertation in the ﬁrst chapter. Breuer. 2004. To be submitted to Physics of Fluids. Chapter 7. Vol. Chapter 5. 2006. reviews of previously published works. Concluding remarks and suggested studies. 2006. with details of experimental methods and results. Yoo and Kenneth S. “Near-surface velocimetry using evanescent wave illumination” by Songwan Jin.This dissertation consists of experimental studies of boundary slip and hindered diﬀusion in the nano-scale. Chapter 2. Experiments in Fluids. hindered diﬀusion and total internal reﬂection velocimetry. The contents of the chapters are: Chapter 1. J Y. Journal of Fluid Mechanics. 566. Including basic concepts of slip ﬂow. Jeﬀrey S. Breuer. and discussions of the main results obtained. Vol. Paper 5. Paper 4. Chapter 6. Breuer. Breuer. 2006. and a collection of journal papers. 447-464. To be submitted to Physics of Fluids. “Direct measurement of slip velocities using three-dimensional total internal reﬂection velocimetry” by Peter Huang. Introduction. each as a subsequent chapter. Peter Huang. pp. iii . Paper 2. “Direct measurement of anisotropic near-wall hindered diﬀusion using total internal reﬂection velocimetry” by Peter Huang and Kenneth S. Paper 1. “Direct measurement of slip length in electrolyte solutions” by Peter Huang and Kenneth S. 825-833. Paper 3. Chapter 3. Breuer. Jinil Park. “Simulations of hindered diﬀusion in shear ﬂow and its implications for near-wall velocimetry” by Peter Huang and Kenneth S. Chapter 4.

Numerous discussions with Professor Tripathi and Professor Thomas Powers during the years on chemistry and statistical mechanics are acknowledged and very much appreciated. Brian Burke. patience and encouragement throughout the years of graduate study. iv . My greatest gratitude goes to my wife. Without his creative ideas and brilliant suggestions many subtleties of experimental methods and results would not have been found. for his introduction of the total internal reﬂection ﬂuorescent microscopy setup. for their generous help in micro-fabrication. the administrative and research supports of Mr. Professor Kenneth Breuer. Mr. Professor Eric Lauga and Professor Anubhav Tripathi. Teng-Fang Kuo. I also would like to thank my dissertation readers. Professor Sylvain Cloutier. my sister and my extended family for their love. Without his encouragement. Charles Vicker and Ms. for their insightful comments during dissertation revisions. Mr. As a lowly ranked graduate student. Jeﬀrey Brown. Michael Jibitsky.I would like to ﬁrst thank my mentor. the projects described in this dissertation would not have been fruitful. Without their kind assistance many research projects would not have moved forward as smoothly as they did. Mr. Jahn Torres. support and best wishes over the years. Brian Corkum. for his guidance and support through my graduate study. Songwan Jin. and for putting up with me during the ups and downs of experiments. for her love. In addition. optical system design and setup. Finally I would like to thank my parents. Jinkee Lee and Matt Kerby. I also would like to thank Dr. Virginia Novak are especially appreciated. A special thank goes to my fellow graduate student and my friend Jeﬀrey Guasto. constructive criticisms and inexhaustible knowledge. I am very grateful to Professor MinJun Kim. nano-scale measurements and sharing of lab equipments.

. . . . .2 THEORETICAL CONSIDERATIONS . . . . . .4 CONCLUDING REMARKS . .3. . . . . . . .Contents 1 Introduction 1. . . . . . . . .3 RESULTS AND DISCUSSION . . . . . . . . . . . 2. . . . . . . . . . . . . .2. . . . . . . . . . . . . . . . . . . . . . . . . 3. . . . .1 INTRODUCTION . . . . . . . . . .1 INTRODUCTION . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . . . . 1 1 3 4 6 8 8 9 12 14 15 18 20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Velocimetry Analysis . . . 2. . . . . . . . . . . . . . . . . . . . . . . 3. 1. . . . . . . . . . . . . . . . . . . . . .1 INTRODUCTION . . . . . . . . . . 3. . . . . . . . .2 HINDERED DIFFUSION . . . . . .4 Measurements of Apparent Slip Velocities . . . . . . . . . . . . . . . . . . . . .3 EXPERIMENTAL PROCEDURES . . . 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . 2 Paper 1: Near-surface velocimetry using evanescent wave illumination 2. . . . . . . . . . . . . . . . . . . . .1 Materials and Setup . . . . . . . . . . . . . . . . . . . . . .3 Comparisons with Numerical Simulations . . . . .2 Streamwise Velocity Analysis . . . . . .3 Near-Surface Shear Flow . . 4 Paper 3: Direct measurement of slip length in electrolyte solutions total . . . . . . . . . . . . . . . . . . . . . 3. . . . . .2 Emission Intensity of Fluorescent Particles . . . . . . . . . . . . .2. . . 2. . . . . . . . . . . . . .4 RESULTS AND DISCUSSION . . . . . . 3. . . . . . . . . . 3. . . . . . . . . . . . . . . . . . . . . . . . 2. . .1 Validation of Intensity Calibration Curve . . . . . . . . . . . . . . 3 Paper 2: Direct measurement of slip velocities using three-dimensional internal reﬂection velocimetry 3. 3. . . . . .4.1 BOUNDARY SLIP . . . . . . . . . . . . . . . . . . . . . . . 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. .3.4 SUBTLETIES OF NEAR-WALL SHEAR FLOW . . . . . . . . . . . . . . 2. 22 22 23 23 24 26 28 28 30 31 31 31 32 34 37 39 5 Paper 4: Direct measurement of anisotropic near-wall hindered diﬀusion using total internal reﬂection velocimetry 43 5. . .1 Cross-stream Velocity Analysis . .4. . . . . . . . . . 3. . . . . . . . .1 Total Internal Reﬂection Microscopy . .3 Velocity Distributions of Particles . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . .4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4. . 3. . . .2 EXPERIMENTAL PROCEDURES . 3.2. . . . . . . . . . . . . . . . . . . . . . . 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 v . . . .5 CONCLUDING REMARKS . . . . . .2 Hindered Diﬀusion . . . . . . . . . . .3. . . . . . . . .3 TOTAL INTERNAL REFLECTION VELOCIMETRY 1. . . . . . . . . . . . . . .

. . . . .5 THEORY OF HINDERED DIFFUSION EXPERIMENTAL PROCEDURES . 6. . . . . . . .3.3. . . . . . . . . . . . . . . . . . . 6. . . . . . . . 6. . . . . . . .2 Eﬀects of Shear on Particle Velocities . . . . .2. . . . . 6. . .4 5. . . . . .3 5. . .3. . . . . . . .1 INTRODUCTION . . . . . . . .2 THEORIES AND COMPUTATIONS . . . . . . . . 6. . . . lack of ) on near-wall submicronparticles 73 C Evanescent wave image of micron-sized ﬂuorescent particles 75 vi . . . . . . . . . . .4 Implementation of Simulation . . . . . . . . .2 5. . . . . . . . . . . . . . . . . . . . . 6. . . . .3 RESULTS AND DISCUSSIONS .4 CONCLUDING REMARKS . . SUMMARY . . . 7 Concluding Remarks and Suggested Studies A Calibration of beam incident angle and its implications for . . . . . . . . . .2 Particle Displacement Due to Hindered Diﬀusion . .2. .4 Horizontal Apparent Velocity Distributions . . . . . . . . . . . . . . . . . 6. . . . . . . . . . . RESULTS AND DISCUSSION . . . . . . . . . . . . . . .1 Sedimentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5. . . . . . . . . . 6. . . . . . . . . . . . . . 44 44 46 49 6 Paper 5: Simulations of hindered diﬀusion in shear ﬂow near-wall velocimetry 6. . . . . . . . . . . . . . . . . . . . . . . . . . .2. . . . . . . . . . . . . . . . . . . . 50 50 51 51 53 54 54 55 55 55 58 60 62 67 68 70 B Shear-induced lift force (or more precisely. .1 The Langevin Equation . . . . . . . . . . . . . . 6. . . . . . . . . . .3. . . . . . . . . .3. . . . . . 6. .3 Particle Drop-in’s and Drop-out’s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Hindered Diﬀusion . . . . . . . . . . .5 Time Evolution of Apparent Velocity Distributions 6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2. . . . . . . . . . 6. .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 Distribution of particle velocity vectors of 200-nm particles . . . . . . . . . . . . .12 3. . . . . . . . . . . . . . . . . . . .5 < I e /I0 < 1 in a uniform concentration ﬁeld . Image acquisition system . . . . Experimental apparent velocity of particles in a shear ﬂow over a hydrophilic surface Experimental apparent velocity of particles in a shear ﬂow over a hydrophobic surface The additional slip length due to surface hydrophobicity . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . Schematic of the experimental setup . . . . . . . . . . . . . .10 Streamwise velocity distribution of 200-nm particles determined from Monte Carlo simulation . . . . . . . .4 2. 2. . . . . . . . . . . . 42 Schematic of total internal reﬂection velocimetry . . . . . . . . . . Observed ﬂuorescent particle intensity distribution and its probability density function (PDF) . . . .3 3. 45 vii . . . . . . . . .10 3. . . . . . . . . . . . . . 40 Measured slip lengths of aqueous solutions . . . . . . . . . . 2. . . . . . . 3. . . . . . . shear rate . . . . . . . .8 3. . . . . .1 3. . . . . .1 4. . . . . . . . . . . . . The ratio of statistical apparent velocity of particles and mean ﬂuid velocity under no slip . . . . . . . . . .9 3. . . . Particle images of diﬀerent illumination methods: wideﬁeld (direct. . . .5 3. . . . . . . . . . . . .7 Cross-stream Brownian motion of particles in an inﬁnite medium and near wall . . . . . . . . . . . . . . . . . . . . .11 3. .11 Streamwise apparent velocity predicted by simulation . . . . . . . . . . . . . . . . . . . . . Fluorescent particle intensity as a function of its distance to the glass surface . . e The predicted position distribution of particles with 0. . . . . . Ratio of hindered diﬀusion coeﬃcients (Dexp ) for Brownian motion parallel to a surface Distribution of observed particle streamwise velocities under various shear rates . .1 Objective-based total internal reﬂection ﬂuorescence microscopy . . Objective-based total internal reﬂection velocimetry (TIRV) system . . . . . . . . . . .1 2.9 Apparent particle velocity vs. . . . . 2. . . . .13 4. . . . . . . . . . . . . . . ﬂood) illumination Particle images of diﬀerent illumination methods: near-wall TIRFM image . . . . 2. Distribution of observed particle streamwise velocities after scaling . . . . . . . . . . . . . . . .1 2. . . . . . . . . . . . . . .7 3. . . . . . . . . .8 Experimentally-measured distribution of streamwise velocities of 200-nm diameter particles . . . . . . . . . . . .6 3. . . . . . . . . . . . . . . . . . . . . . The emission intensity distribution of particles in a uniform concentration ﬁeld .2 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 10 11 12 13 13 14 15 16 17 19 20 24 25 26 27 29 30 31 32 33 34 35 36 36 Schematic of objective-based TIRFM . . . . . . . . . 2. . . . . . .4 3. . . . . . . .2 5. . . . . . Schematic of near-wall particles moving near the surface illustrating the observation range . . .3 2. . . . . . . . . . . . . .2 2. . . . . . .5 Schematic of total internal reﬂection ﬂuorescence microscopy .List of Figures 1.

3 Plot of laser beam angle vs. . . . . . . .4 COMSOL simulation of a particle with d/λ = 0. . . . . . . . C. . . . .3 6. . Time evolution of apparent velocity distribution . . .15 Intensity calibration of 1. . Collapsed apparent velocity distribution of particles at various imaging range . . .10 Cross-sectional intensity proﬁle of a 6-µm particle (d/λ = 12) . . . . .2 6. . . . . . Particle displacement distribution due to hindered diﬀusion . . . . . . . . . . . . . . . . . . . . . . . . . . 47 A schematic of the simulation geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12 6. Spatial distribution of particles from a ﬁnite layer at various times . . . . . . . . . . . .1 Schematic of laser beam refraction at the glass/air interface . . . 71 A. . . . . . . . . . . . . Sedimentation of small particles . . 72 C.9 Digital image of a 3-µm particle (d/λ = 6) in contact with glass surface C. . . . . .2 5. . . . . . . . C.3 Intensity decay of evanescent ﬁeld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39 in evanescent ﬁeld . . . . . . . . .11 6. . . . . . . . . . . C. . . . . . . . . . C. . . . .6 6. . . . . . . . .5 COMSOL simulation of a particle with d/λ = 6 in evanescent ﬁeld . . . 46 Hindered diﬀusion correction vs. . . .1 6. . . . . . . . . . . . . .7 6. . . . . . . .14 6. . . . . . . . . . . . . . . . . . . . . .5. . C. . Sedimentation of large particles . . . . . . . . . . . . . . . . . . . . . .5 6.13 6. . . converging lens position . . . . . . . . . .7 Overall evanescent energy in the suspended particles . . . . . . . . . . . . C. . . . . Normalized apparent velocity distribution of particles in a ﬁnite imaging range Apparent velocity distribution of particles from various imaging ranges . . Rescaled time evolution of mean particle apparent velocity . . . . .8 6. . particle/glass gap size . . . . . . . . .1 Schematic of COMSOL simulation geometry . . . . . . . . . . . Apparent velocity distribution of particles remaining in a ﬁnite imaging range . . . . . Schematic of potential paths for particle translation . . . . . . . . . . . . . . . 76 76 77 77 78 78 79 80 81 82 82 viii . . . . .9 6. . . . . 71 A. .8 Cross-sectional intensity proﬁle of a 3-µm particle (d/λ = 6) . . . . . . . Percentage of particles remaining in imaging range . . . . . . Time evolution of mean particle apparent velocity . . Spatial distribution of small particles due to hindered diﬀusion .5-µm radius ﬂuorescent particles in evanescent ﬁeld . C. . . . . . . . . . . .4 6. . .3 6. 52 56 57 58 59 59 60 61 61 62 63 63 64 65 66 A. . . . . .6 COMSOL simulation of a particle with d/λ = 12 in evanescent ﬁeld . . . . .10 6. . C. . . . . .2 Photo and schematic of beam incident angle measurement . . . . . . . . . . . . . . . . . . . . .2 COMSOL simulation of total internal reﬂection . . . . . . . . . . . . . . .11 Digital image of a 6-µm particle (d/λ = 12) in contact with glass surface . C. . . . . . . . . .

. . 53 Representative values of the non-dimensional time between consecutive image acquisition . . . . . . . .1 6. . . . .2 Sample values of the Peclet number and the sedimentation coeﬃcient . . . . . . . . . . . . . . . . . . . . . . . . . .List of Tables 6. 53 ix . . . . . . . . . . . . . .

17]. suspended particulates and the solid surface. investigations into its application in biotechnology has been the most intense. [19] calculated that the ratio of slip velocity to bulk velocity becomes very small if the channel height is more than a few hundred micrometers. Even though the idea of a slip ﬂow has been considered by scientists as early as Newton [18]. Thus the majority of interesting surface-induced physical phenomena occur in the near-surface region of the ﬂuid phase and can be categorized into two groups: (1) changes of the ﬂuid mechanical characteristics due to the presence of the solid surface. In particular. slip ﬂow [7] and surface chemistry directed ﬂow [8. (2) interactions between the dissolved molecules. the existence of boundary slip in a Newtonian liquid has been a controversial topic. the high surface-area-tovolume-ratio also means that near-surface phenomena will have a much larger inﬂuence on the bulk of the ﬂuid content. while particle or cell adhesion [10] and detachment [11]. The strong experimental support of such assumption could be due to the fact that the magnitude of slip velocity was much smaller than the measuring instrument accuracy and thus remained undetectable. the solid boundary is viewed as rigid and inert such that physical and structural changes due to ﬂuidic forces are nonexistent. 1. for chemical reactions whose reaction sites are at solid surfaces. increased hydrodynamic drag [12]. In both cases. Microﬂuidic devices are very attractive in biotechnology over conventional technology because they require small sample volume and produce rapid results. Examples of physical phenomena in the former group include electrokinetic ﬂow [6]. empirical data up to the late twentieth century had deemed it negligible.Chapter 1 Introduction Since the introduction of the ﬁrst microﬂuidic device. Unlike polymer solutions whose slip behaviors have been thoroughly investigated [15. Under most circumstances. content sorter [3] and drug delivery [4]. Westin et al. these miniaturized ﬂuidic manipulation systems have been regarded as one of the most promising technologies of the late twentieth century. for example the viscous drag on the channel walls. the high surface-area-to-volume-ratio characteristic of microﬂuidics oﬀers a much higher eﬃciency [5]. Another possibility is the relatively insigniﬁcant impact of slip on the ﬂuid bulk ﬂow in the macroscopic scale. Indeed. On the other hand. electrostatic interactions [13] and eﬀects of depletion layers [14] are eﬀects of the latter group. Therefore when macroscopic ﬂow measurements 1 .1 BOUNDARY SLIP One of the ﬂuid mechanics questions that have remained unanswered over centuries is the slip ﬂow and its origin. 9]. 16. understanding of interactions between the ﬂuid content and the solid boundary is critical in designing and analyzing microﬂuidic devices. reagent mixing [2]. Examples of such applications include immunosensors [1].

(1. In some of these experiments. 32]. demonstrating the potential of the TIRV technique in making direct measurements of slip velocities. 31]. With measurements conducted at glass surfaces of sub-nanometer surface roughness. 23. which is based on the Navier hypothesis that the velocity of a ﬂuid at a solid surface is proportional to the shear stress. 31. because some earlier experiments [20. 27] or shear-independent [20. Although it is generally agreed among research ﬁndings that surface hydrophobicity aids slip eﬀect [25. with varying degrees of accuracy and uncertainty. These experimental studies produced various magnitudes and dependencies of boundary slip.1) γs ˙ where Uslip is the slip velocity and γs is the ﬂuid shear rate at the solid surface. and an additional slip length of 16 nm is found attributable to surface hydrophobicity. a qualitative conclusion is reached that surface slip length of an aqueous solution would be small and surface chemistry-dependent. [28] to calculate slip velocities.2 were conducted slip eﬀect could be hardly noticeable. hundreds of nanometers [29. [27] and Cottin-Bizonne et al. 30. Experimentally ˙ measured slip lengths were reported to range from micrometers [20. slip velocity was indirectly inferred from measurement of other physical quantities. Although a quantitative conclusion of slip length magnitude could not be drawn due to the uncertainty in determination of the exact imaging range. The accuracy of slip measurements is further improved with the implementation of threedimensional tracking in the TIRV technique. Uslip δ= . again the magnitude of such an eﬀect remains controversial. In the past decade slip ﬂow began to receive more attention again. 30]. [29] and micro-scale particle image velocimetry (µPIV) by Tretheway & Meinhart [30] and Joseph & Tabeling [31]. In Paper 2: Direct measurement of slip velocities using three-dimensional total internal reﬂection velocimetry (chapter 3). several physical factors that are suspected of inducing slip are also examined. to be introduced later) in performing near-surface measurements makes it a perfect technique for direct observation of slip velocities in a shear ﬂow. That is. 29. . Since then many experimental attempts were made to conﬁrm the existence and the magnitude of slip velocities. we report on a slip length of deionized water being less than 100 nm. 25. [25] to infer slip velocity. The ability of total internal reﬂection velocimetry (TIRV. In Paper 1: Near-surface velocimetry using evanescent wave illumination (chapter 2). it is shown that velocities of ﬂuid elements within a few hundred nanometers from a solid surface can be accurately measured. δ. Disagreement also exist on whether the slip behavior is shear-dependent [21. In this report. Of particular interest to microﬂuidics is aqueous solution slip over diﬀerent surface conditions as water is the most common solvent in biological and chemical applications. 28. while the forces required to move two surfaces separated by a thin ﬁlm of the test ﬂuid were employed Zhu & Granick [26]. and a slip length above a few hundred nanometers is unlikely. For instance. the relationship between applied pressure drops and measured ﬂow rates was used by Choi et al. 26. Others took a direct approach of studying slip by measuring near-surface ﬂow velocities. 33] to less than 100 nanometers [25. Neto et al. 24] have reported slip boundary conditions in Newtonian liquid. In conducting this experiment. Examples of the direct measurements include ﬂuorescence recovery after photobleaching (FRAP) by Pit et al. 32]. 21] and molecular dynamics simulations [22. The commonly used formulation to characterize boundary slip is the slip length. 28. 27. the obtained slip length values agree with the surfaceroughness dependency previously reported by Granick et al. we report on our ﬁrst attempt to measure slip velocities of deionized water using the TIRV technique. 26. [34] The issue of apparent slip caused by nano-bubbles at the glass surface is additionally disputed with experiments conducted with sub-nanometer surface roughness and degassed test ﬂuids.

3 Still, questions remained on whether other physical forces, particularly the electrostatic and electrokinetic eﬀects proposed by Lauga et al. [7, 35], would lead to false slip results in TIRV measurements. We address such a concern in Paper 3: Direct measurement of slip length in electrolyte solutions (chapter 4), by repeating the slip measurements with electrolyte solutions whose ionic concentrations have been predicted to reduce the apparent slip eﬀect to sub-molecular level. It is observed that the presence of electrolytes has no eﬀect on the measured slip lengths, suggesting that the observed slip velocities are most likely not due to electrostatic and electrokinetic eﬀects, but are consequences of true boundary slip.

1.2

HINDERED DIFFUSION

Another near-surface phenomenon with great ﬂuid mechanical and mass transport implications is hindered diﬀusion of colloidal particles. The concept of near-wall hindered diﬀusion stems from an increased frictional coeﬃcient on a near-wall object. Einstein proposed that the diﬀusion coeﬃcient of a colloidal object is the ratio of the ﬂuid thermal energy to the object’s frictional coeﬃcient in Stokes ﬂow. Thus if a particle experiences an increase in ﬂuidic friction as it approaches a solid wall, its diﬀusive translation or Brownian motion will be hindered. Brenner [36] and Goldman et al. [37, 38] were the ﬁrst to analytically solve the increased frictional coeﬃcients of a near-wall sphere with a lubrication formulation. Their results were later re-conﬁrmed by Chaoui & Feuillebois [12] with an spherical harmonics expansion method. Besides being a ﬂuid mechanics theory, hindered diﬀusion has additional implications in chemical engineering and drug delivery systems since diﬀusion is the dominant mass transport mechanism in microﬂuidics. Because of its signiﬁcance, advancement of near-surface measurement techniques had lead to several experimental studies of hindered diﬀusion. Employed experimental techniques include evanescent light scattering oﬀ freely suspended particles by Bevan & Prieve [39], evanescent light-scattering spectroscopy by Hosoda et al. [40], catch-and-release video microscopy with optical tweezers by Lin et al. [41], evanescent light scattering coupled with optical radiation pressure by Oetama & Walz [42] and three-dimensional ratiometric total internal reﬂection ﬂuorescence microscopy with nanoparticles by Banerjee & Kihm [43]. Most of these studies have reported hindered diﬀusion coeﬃcients agreeing to values derived from the theories of Brenner and Goldman et al. In the theories of Brenner and Goldman et al., the increased friction factor is a function of particle radius and gap size between the particle and the solid wall. Unlike in the ﬂuid bulk, the ﬂuidic friction also becomes anisotropic in the near-wall region. In other words, the hindered diﬀusion coeﬃcient is diﬀerent for directions normal and parallel to the solid surface. Few studies have attempted to measure such anisotropicity simultaneously due to experimental limitations. Lin et al. [41] demonstrated such anisotropicity for particles whose gap-size-to-radius ratio is greater than one, and found hindered diﬀusion coeﬃcient values agreeing with theories. Another study that reported anisotropic hindered diﬀusion coeﬃcients for gap-size-to-radius ratio greater than one was conducted by Banerjee & Kihm [44]. However, their study reported that the measured diﬀusion coeﬃcient in the direction normal to the solid wall agreed with the theoretical values only when large particles were tested. By applying the 3D-TIRV technique to freely suspended micron-sized ﬂuorescent particles, we aim to simultaneously observe the three-dimensional anisotropic hindered diﬀusion for gap-size-toradius ratio much less than one. The theory under this condition is vastly diﬀerent from that of the gap-size-to-radius ratio greater than one, and based on our literature survey no such experimental conﬁrmation of the theory has been reported. In Paper 4: Direct measurement of anisotropic

4 near-wall hindered diﬀusion using total internal reﬂection velocimetry (chapter 5), we demonstrate that the three-dimensional tracking technique of TIRV can be adopted into 3D displacement measurements of freely suspended 1.5-µm radius particles. The displacement measurements reveal that the hindered diﬀusion coeﬃcients are in close agreement with the theoretical values predicted by the asymptotic solutions of Brenner and Goldman et al. for gap-size-to-radius ratio much less than one, and hindered diﬀusion anisotropicity is simultaneously demonstrated in all data sets.

1.3

TOTAL INTERNAL REFLECTION VELOCIMETRY

With so much interest in near-surface phenomena, researchers have developed various techniques to study them. Optical microscopy has been widely used to observe interactions in the micrometer scale. However, as fabrication technology advances, the deﬁnition of “near-surface” has also evolved from microscopic and to the nano-scale. Traditional optical techniques are no longer suﬃcient now because the visible wavelength is the physical limit of optical resolution (∼ 0.5 µm). A frequently used technique to overcome this obstacle is evanescent wave imaging [45]. In this technique, a beam of collimated laser light is brought to a solid/liquid interface through the solid phase at a large incident angle, as shown in ﬁgure 1.1. Since solids typically have higher indices of refraction than ﬂuids do, total internal reﬂection occurs at the interface if the incident angle is greater than the critical angle predicted by Snell’s Law. In fact, at the nano-scale this reﬂection is not “total”, but a small fraction of energy, called evanescent waves, extends into the ﬂuid phase. In the ﬂuid phase the evanescent wave energy or intensity, I, decays exponentially with distance, z, away from the two-medium interface by I(z) = I0 e−z/p , (1.2) where I0 is the intensity at the interface and p is known as the evanescent wave penetration depth. The penetration depth, which characterizes the length scale of the evanescent ﬁeld, can be calculated from λ0 2 2 −1 p= ns sin θ − n2 2 , (1.3) l 4π where λ0 is the wavelength of the incident light, θ is the beam incident angle and ns and nl are the refractive indices of the solid and liquid, respectively. For visible light, the evanescent wave energy decays to zero within a few hundred nanometers. Thus by using the evanescent wave as an illumination source, one can observe dynamics of ﬂuids and suspended particulates within a few hundred nanometers from the solid surface, while contents outside of this layer would remain invisible. Consequently near-surface phenomena can be observed with clarity and without the interfering noise contributed from objects in the ﬂuid bulk. Since the 1970’s, biologists have combined ﬂuorescence and evanescent wave imaging in studying near-surface biological events [46, 47]. Termed “total internal reﬂection ﬂuorescence microscopy” (TIRFM), this technique allows observation of ﬂuorescently labelled samples placed in the evanescent ﬁeld and under a high magniﬁcation microscope. Fluorescence is a quantum optical eﬀect of a unique group of molecules called ﬂuorophores, whose quantum states can be excited by a speciﬁc range of visible light and release photons of a longer wavelength after initial excitation. Their molecular sizes are excellent for probing near-surface regions at the nano-scale. Examples of TIRFM include the previously mentioned ﬂuorescent recovery after photobleaching (FRAP) and ﬂuorescence resonance energy transfer (FRET). In FRAP, the ﬂuorophores of a chosen spot inside the microscope ﬁeld of view is purposely photobleached with a high power laser beam. The light-emitting ﬂuorophores in the surrounding area will diﬀuse into this “dark” spot immediately following the photobleaching. By measuring the diﬀusivity of these light-emitting ﬂuorophores, one

5

z

liquid ~ penetration depth

θ

solid

Figure 1.1: Schematic of total internal reﬂection ﬂuorescence microscopy (TIRFM). A ﬂuorescent particle suspended in water was placed in an evanescent ﬁeld. If the illumination beam incident angle, θ, is greater than the critical angle predicted by Snell’s law, total internal reﬂection occurs at the solid/liquid interface. The evanescent energy then illuminates the encapsulated ﬂuorophores inside the particle. can study the targeted molecule mobility. For instance, FRAP has been reported in measurement of protein mobility and activity in living cells [48]. FRET, on the other hand, takes advantages of a quantum energy transfer that occurs between matched ﬂuorescent molecules of two diﬀerent wavelengths [49]. Because such energy transfer can only occur if the two molecules are less than 10 nm apart, they oﬀer an opportunity to examine interactions in the molecular level. Surprisingly, a long time had passed before physical scientists ﬁnally caught up with the merits of evanescent wave imaging. At ﬁrst, evanescent energy scattered oﬀ non-ﬂuorescent suspended particles was used in quantitative measurements of near-surface dynamics. Such experimental studies include measurement of surface charge densities on suspended particles by von Grunberg et al. [50], quantifying double-layer repulsion between a colloidal particle and a glass substrate by Flicker et al. [51], eﬀects of particle size on near-wall particle depletion by Kok et al. [14], charged particle adsorption by Kun & Fendler [52], and hindered diﬀusion by Bevan & Prieve [39]. Only in the past decade were ﬂuorescent tracer particles used in microscopic dynamics measurements. Particle-based velocimetry has long been used in ﬂuid visualization and measurement [53]. It is based on an intuitive and for most part correct assumption that the seeding tracer particles are carried by the ﬂuid surrounding them, and therefore their translational velocities must be that of the local ﬂuid elements. Apparent velocities of the tracer particles are calculated based on displacements of the tracer particles and the time between successive particle imaging. When particle-based velocimetry methods were adopted to study microﬂuidics, sub-micron ﬂuorescent tracer particles were used to minimize light scattering and imaging noise while attaining spatial resolutions of tens of nanometers [54]. Santiago et al. [55] were the ﬁrst to demonstrate a correlation-based microscopic particle image velocimetry (µPIV) to map out a velocity ﬁeld around a Hele-Shaw cell. In their experiment, cross-correlation analysis was performed on successive images of ﬂuorescent tracer particles to identify the most probable ensemble displacements. Since their report, µPIV has been the work horse among diagnostic techniques of microﬂuidics. When applying to near-surface measurements, µPIV does suﬀer a major drawback. Its resolution in the direction perpendicular to the imaging focal plane is limited by the focal depth of the

6 microscope objective lens and is at least 0. Both slip and hindered diﬀusion studies demonstrate the applicability and versatility of the TIRV technique in making near-wall particle velocity and displacement measurements. we present a technique. In Paper 2: Direct measurement of slip velocities using three-dimensional total internal reﬂection velocimetry (chapter 3).5-µm radius ﬂuorescent particles.5 µm from a solid surface. In Paper 2: Direct measurement of slip velocities using three-dimensional total internal reﬂection velocimetry (chapter 3) and in Paper 3: Direct measurement of slip length in electrolyte solutions (chapter 4). Zettner & Yoda’s nano-PIV is undoubtedly a novel technique. 100.4 SUBTLETIES OF NEAR-WALL SHEAR FLOW As previous discussion have emphasized. Since the statistical analysis of nano-PIV does not make an attempt to treat the drop-in’s and drop-out’s. owing to the sensitivity of evanescent wave imaging. Zettner & Yoda [56] overcame µPIV’s deﬁciency by combining it with evanescent wave illumination. Under evanescent wave imaging. further improving its accuracy and applicability. 1. The short eﬀective range of evanescent wave allowed them to measure ﬂuid velocities that were within 280 nm from a solid surface. In Paper 4: Direct measurement of anisotropic near-wall hindered diﬀusion using total internal reﬂection velocimetry (chapter 5). and thus the same three-dimensional particle tracking principle applies. Brownian motion of particles in the near-surface region is a non-negligible mechanism and has signiﬁcant implications in the accuracy of near-wall velocimetry. Brownian motions of the particle ensemble can be monitored and statistically analyzed. it is unsuitable if diﬀusive dynamics is of interest. Thus numerical approaches oﬀer insightful alternatives to explore the subtleties of near-wall ﬂow. or events where particles diﬀuse in and out of the evanescent ﬁeld between consecutive frames. we extend the TIRV technique to three-dimensional. the TIRV technique is extended to observing anisotropic near-wall hindered diﬀusion of 1. Li et al. where quantitative measurement can be performed on events that occur within 100 nm from the surface.and 200-nm radius ﬂuorescent particles are employed in 3D-TIRV experiments to measure slip lengths over hydrophilic and hydrophobic surfaces. and thus a particle’s peak intensity can be used to infer its distance from the solid surface. called “total internal reﬂection velocimetry” (TIRV). the peak intensity of these large particles follow an exponential decay relation that is also identical to the exponential decay of evanescent energy. Many of the issues that need to be considered. we use the TIRV technique to measure aqueous solution boundary slip and near-surface hindered diﬀusion of spherical particles. Secondly. [57] further extended this nano-PIV technique into a multilayer correlation analysis. Consequently. By combining TIRFM with tracking of individual tracer particle. as an alternative to nano-PIV in near-surface measurements. However it still has two signiﬁcant limitations. could not be easily assessed through experimental data. because diﬀusion is treated as measurement noise in the cross-correlation analysis of the nano-PIV.5 µm [31]. In Paper 1: Near-surface velocimetry using evanescent wave illumination (chapter 2). µPIV could not distinguish physical features within 0. however. Firstly. The analysis of the image data reveals that a statistical approach is needed in making near-surface velocimetry measurement even for particles whose size variation is as small as a few percent. signiﬁcant measurement errors could persist. The main concern in near-wall velocimetry is the ensemble behavior of tracer particles in the . As mentioned previously. It is observed that the peak intensity of a ﬂuorescent particle decays exponentially in the same length scale as the evanescent wave energy. leading to a more accurate accounting of all contributing particles. rapid Brownian motions of nanoparticles could lead to a large amount of particle “drop-in” and “drop-out”.

. Sadr et al. the relative strengths of near-wall shear and diﬀusive forces are explored through Brownian dynamics simulations. how such ensemble behavior aﬀects the accuracy of velocity measurements. hindered diﬀusion causes an under-estimation of ﬂuid velocity due to biased sampling of tracer particles very close to the wall. this approach has been used in studying the binding rates between attached molecules [60]. a signiﬁcant portion of the tracer particles would sample planes of higher velocities. ensemble behavior of particles can be obtained through statistical analysis of a large number of repeated simulations. it is found that if the time interval between successive particle image acquisitions is short. and more importantly. however. With a proper time step size. the results found in the Brownian dynamics simulation oﬀer a way where the true ﬂuidic velocities can be inferred from particle apparent velocities through proper scaling. colloidal particle deposition in a microchannel ﬂow [61]. However. initial and boundary conditions. The same Brownian dynamics simulation also provides a tool to assess the eﬀects of hindered diﬀusion and wall presence on various near-wall velocimetry techniques. The other approach takes advantage of the Langevin equation in which the displacement of a particle consists of a deterministic component (such as displacement of the suspending ﬂuid) and a stochastic component (such as Brownian motion). asymmetric shape and width of apparent velocity distributions are attributed to the shear eﬀect. Still. the time evolution of the particle ensemble phase space conﬁguration function is computed through numerical solution of the momentum-position partial diﬀerential equations. Recently. accuracy of potential energy proﬁles determined by evanescent wave scattering [62] and the accuracy of nano-PIV [63]. respectively. In the Fokker-Planck approach. This scaling method. In addition. In Paper 5: Simulations of hindered diﬀusion in shear ﬂow and its implications for near-wall velocimetry (chapter 6). Two equally viable numerical approaches have been proposed to study Brownian motion-related problems [58]. is available only for TIRV but not for nano-PIV. The combined eﬀect of the observations described above is that near-wall particle-based velocimetry measurement is not time-invariant. We are most interested in the ensemble behaviors of near-surface particles in a shear ﬂow. Its intuitive resemblance to a physical velocimetry experiment has gained some popularity in colloidal studies. resulting in an over-estimation of overall ﬂuid velocity. Particle drop-in’s and drop-out’s. The ensemble behaviors are then obtained from probability analysis using the phase space conﬁguration function. are found to be a potential source of measurement error for nano-PIV because of the rapid Brownian motion of nanoparticles.7 time interval between consecutive image acquisitions. making TIRV the more superior method in near-surface measurements. [59] had taken the Fokker-Planck approach to study the diﬀusion-induced bias in near-wall velocimetry. Also called Brownian Dynamics (BD) simulations for its direct emulation of Brownian motions. and the eﬀects of the wall presence and hindered diﬀusion on the measured velocities because these are issues that we have noticed during our TIRV measurements of boundary slip and anisotropic hindered diﬀusion. With diﬀusive time and particle radius as time and length scales. and we believe it can lead to signiﬁcant inaccuracy in nano-PIV if not treated appropriately. It is observed that the shear force dominates over diﬀusion at P e > 3. if the time interval between successive particle image acquisitions is long.

1 INTRODUCTION Over the past few years. slip measurement techniques can be classiﬁed into indirect and direct methods.Chapter 2 Paper 1: Near-surface velocimetry using evanescent wave illumination Total Internal Reﬂection Velocimetry (TIRV) is used to measure particle motion in the near-wall region of a microﬂuidic system. The results suggest that the slip length. the no-slip boundary condition. 21. 2. There are also other groups of researchers who attempted to understand the slip phenomenon from 8 . but uncertainty regarding the exact character of the illumination ﬁeld prevents a more accurate measurement at this time. if present. fabrication and performance of these devices. is less than 25 nm. the ﬂow rate and pressure within the ﬂow duct [20. The statistical diﬀerence between velocities measured over hydrophilic and hydrophobic surfaces was found to be minimal. studies regarding near-wall ﬂuid motion have intensiﬁed because of the emergence of micro-electro-mechanical-systems (MEMS). In general. a velocity. Issues associated with the accuracy of the experimental technique and the interpretations of the experimental results are also discussed. In the indirect methods. proportional to the shear rate was observed. Numerical simulations are presented to help understand the results and to provide insight into the mechanisms that result in the experimentally observed distributions. where the ﬂuid-surface interaction is important to the design. a better understanding of ﬂuid-surface interaction becomes necessary in designing applicable devices. In particular. slip velocity is inferred from other measurements. now receives a great amount of attention in microﬂuidics. 25]. Sub-micron sized ﬂuorescent particles suspended in water are used as seed particles and their images are analyzed with a PTV algorithm to extract information about apparent slip velocity. TIRV images are illuminated with the evanescent ﬁeld of an incident laser pulse and contain only particles that are very close to channel surface. Thus. many biological applications of microﬂuidic devices require surface coatings that change the wetting ability of aqueous or biological ﬂuids. Examples of the direct measurement methods include hot ﬁlm anemometry [32]. At relatively low shear rates (less than 2500 sec−1 ). total internal reﬂection-ﬂuorescence recovery after photobleaching (FRAP) [29] and micro-PIV [30]. or from forces required to move the surfaces [64]. Moreover. for example. Many experimental techniques have been applied to study the eﬀect of slip on both hydrophilic and hydrophobic surfaces. which has long been experimentally veriﬁed in macroscopic ﬂow.

Similarly. Recently. (2. I. vesicle fusion and single-molecule observation [65. (2. One characteristic of the evanescent wave is that its intensity. such as cell-substrate contacts. The TIRFM technique has long been used in biological studies. 67]. the intensity of an evanescent wave decays exponentially with distance z away from the two-media interface I(z) = I0 e−z/d . images taken under evanescent wave illumination have low background noise. In particular. The maximum incident angle which can be achieved by using an objective lens is given by θmax = sin−1 (N A/nglass ) . and the presence of ﬂuorescent molecules or particles suspended in the sample ﬂuid for imaging and measurement. The ﬁrst method utilizes a prism to guide the laser beam into the glass cover slip. There have also been several recent experimental studies of ﬂuid mechanics by applying evanescent wave illumination [29. which characterizes the evanescent ﬁeld. which can be derived from Snell’s Law. can be calculated as: d= λ0 2 2 n sin θ − n2 2 4π 1 1 −2 . 2. It takes advantage of the fact that total internal reﬂection occurs when light travels from a dense medium (such as a glass cover slip) with refractive index n1 into a less dense medium (such as the sample ﬂuid) with refractive index n2 . allowing total internal reﬂection to occur. The results from these studies are quite diverse. which then serves as a waveguide. the dependence of the slip on the applied shear rate is also a matter of debate with some results suggesting a constant slip length. while others reporting a slip length dependent on shear rate and/or surface hydrophobicity. The other method. decays exponentially with respect to the distance from the two-media interface. which is prismless. Thus. A particle tracking velocimetry (PTV) technique is applied to track particle displacements and ﬂow velocities near the wall.9 a theoretical perspective through molecular dynamics simulations [22. In this paper. Zettner and Yoda [56] used the PIV technique combined with evanescent wave illumination to measure near-surface velocity ﬁeld in rotating Couette ﬂow. 24]. in which the TIRFM technique is applied to observe particle motion in the close vicinity of microchannel walls with diﬀerent surface wetting properties. 2. has the illuminating laser beam directed through a high numerical aperture (NA) microscope objective at an angle that creates total internal reﬂection at the glass-sample interface. 23. 56. This parallel light wave is known as the “evanescent wave”. 68].3) . When total internal reﬂection occurs. The penetration depth. (2. we describe the Total Internal Reﬂection Velocimetry (TIRV) technique. a novel technique termed total internal reﬂection ﬂuorescence microscopy (TIRFM) has been applied to near-wall ﬂuid measurements. as shown in Fig.2) where I0 is the light intensity at the interface and d is known as the evanescent wave penetration depth. Two diﬀerent optical conﬁgurations are commonly used to create an evanescent ﬁeld close to the glass-sample interface.2 EXPERIMENTAL PROCEDURES TIRFM requires the creation of total internal reﬂection of a laser beam at the glass-sample interface. and “apparent slip” lengths ranging from nanometers to microns have been reported. 66.1) As mentioned before. Total internal reﬂection occurs if the incident angle is larger than the critical angle θc = sin−1 (n2 /n1 ). some fraction of the light energy penetrates into the less dense medium and propagates parallel to the surface. showing clear features of sample structure that is near the interface.1.

respectively. 2. depending on shear rate). The coating process was performed in a nitrogen gas chamber to avoid bulk polymerization.3 ms.33) ~ Penetration depth Glass (n = 1.51) Immersion oil Objective lens Figure 2. 5 nsec laser pulses to illuminate the ﬂow. the experimental setup had a critical angle θc = 61. and baked at 100◦ C on a hotplate for a few hours. patterned PDMS channel to create a hydrophobic microchannel. The laser heads were timed to ﬁre with a pre-determined pulse separation (1. At incident angles equal to or larger than θc . illustrated in Fig. and was made permanent after the glass was rinsed in hexane and ethanol. creating an evanescent wave ﬁeld. They were bonded to the test surface after exposure to an oxygen plasma which renders both the glass and PDMS surfaces highly hydrophilic for a short time during which they bond on contact.1: Schematic of objective-based TIRFM. Following bonding. one can choose appropriate laser wavelength and microscope objective or prism to achieve desired penetration depth. The coated glass was bonded to a cleaned. Based on these calculations. In the present experiment. The test cell consisted of a precision glass cover slip on which a polydimethylsiloxane (PDMS) microchannel was attached. 250±1 µm wide and 25 mm long. To create hydrophobic microchannels.4◦ . we have adopted the prismless TIRFM method.2. It has been reported that surface roughness can . the laser beam could be totally reﬂected oﬀ the water-glass interface. the channels were immersed in deionized-water to maintain their hydrophilic surface characteristics. The beams were focused oﬀ-axis at the back focal plane of a Nikon PL Apo NA 1.1 to 3. With water as the sample ﬂuid.4.10 Fluorescent particle solution U z x θ Water (n = 1. it is necessary to coat the glass surface with a transparent and hydrophobic substance because glass is naturally hydrophilic. A dual head Quantel Brilliant Q-Switched Nd:YAG laser was used to generate a pair of 532 nm.9◦ . λ0 = 532 nm and NA = 1.4 100X oil immersion objective lens mounted on a Nikon Eclipse TE200 inverted epi-ﬂuorescent microscope. Because the laser beam is focused oﬀ-axis. dried in nitrogen. illuminating two images for use in a Particle Tracking Velocimetry (PTV) analysis. where λ0 is the wavelength of the incident light and n1 and n2 are the indices of refraction for glass and water. With a water-glass interface. it can be calculated that the penetration depth is approximately 150 nm when the incident angle is θ = 63. We coated glass by immersing glass into a 5-mM octadecyltrichorosilane (OTS) solution (dissolved in hexadecane) at room temperature for several hours. A self-assembled monolayer (SAM) of OTS formed on the glass surface. The PDMS channels were fabricated using standard “soft lithography” techniques [69] and measured 31±1 µm deep. the beam incident angle at the glass-ﬂuid interface can be controlled by changing the radial location of the laser beam.

h2 w (2. the shear rate was estimated from the applied volume ﬂow rate. Thus. at ﬂow rates ranging from 0. Measurements were taken at several shear rates.04% volume fractions respectively. 5 nsec pulse 1.35%).and 300-nm particles. respectively [55].3.8 and 43. Near-wall particle images were projected onto a Q-Imaging Intensiﬁed Retiga CCD camera. Particle solutions were ﬂowed through the test channels using a Harvard Apparatus 22 syringe pump.1 µm. Monodisperse Fluorescent Polymer Microspheres (Duke Scientiﬁc) with diameters of 200 nm (±5%) and 300 nm (±3%). The recorded image pair was ﬁnally analyzed with a PTV algorithm written in our group using the MATLAB programming environment.3 nm in the ﬂow channel and the diﬀraction-limited spot size is 30. The polished Pyrex glass wafer was measured to have a surface RMS roughness of 2 nm. strongly inhibit boundary slip by transferring momentum if liquid molecules are trapped inside the holes of the monolayer [29]. An air gap between the piston and the ﬂuid in the syringe and long tubes were used to dampen pulsations from the syringe motion. Q.6 to 6. the image diameters are 36. were used as seed particles in this experiment. For 200. an atomic force microscope (AFM) measurement of glass surface roughness was also performed. The choice of Particle Tracking Velocimetry (PTV). Under 100X magniﬁcation. NA = 1.3 ms separation Nd-YAG laser 532 nm Dichroic mirror and Barrier filter Convex lens Computer ICCD 1360 x 1036 x 12 bit Pulse generator Figure 2. while the same wafer had a surface roughness of 4 nm after OTS-coating. each image pixel corresponds to 64.1 .4 Objective lens 532 nm.11 PDMS channel Syringe pump 100X.02% and 0. rather than Particle Image Velocimetry (PIV) is an important one and this will be re-addressed later on. suspended in pure water at 0. These microspheres have a peak absorption wavelength of 542 nm and emit a red visible light at 612 nm. Typically 200 image pairs were recorded for each ﬂow condition. For the results presented here. assuming steady laminar ﬂow of an incompressible ﬂuid between two parallel plates without wall slip γwall = ˙ du dy = wall 6Q .9 µm [70].2: Schematic of the experimental setup.4) . which has a capacity of recording 1360-pixelsby-1036-pixels 12-bit images.0 µL/min (±0.

eliminates much of the background noise because the evanescent light penetration depth is restricted to approximately 150 nanometers. Typically about 10-20 particles were identiﬁed in each image. This threshold value allowed us to detect almost every particle which can be identiﬁed with the naked eye and restricts the analysis to particles that are well within the evanescent ﬁeld and in focus. and particles in the bulk ﬂuid are not illuminated. where h is the channel depth and w is the channel width.5.3 and 2. The number of particles identiﬁed in one image is not very sensitive to the exact threshold value. several hundred image pairs at various low shear rates were taken for subsequent PTV image analysis. In this study. on the other hand.12 Figure 2. ﬂood) illumination and evanescent ﬁeld illumination. A large amount of background noise is observed in the case of direct illumination. It is important to point out that the determination of an intensity threshold sets an observation range. The lower bound of the observation range is the particle radius. for the current experiments.3: Particle images of diﬀerent illumination methods: wideﬁeld (direct.4 compare particle images of wideﬁeld (direct. although approximately 50% of these were not tracked between images due to out-of-plane diﬀusion which causes particles to enter and leave the observation region. . as illustrated in Fig. the shear rate could be slightly lower than is estimated here [25]. the intensity threshold was set at 50% of the brightest particle intensity (usually about 1500-2000 counts from a 12 bit CCD camera). However.3 RESULTS AND DISCUSSION Figures 2. To measure particle velocities near the channel surface. If there is signiﬁcant slip at the wall. any possible slip velocity is so small that this uncertainty can be neglected (this presumption will be conﬁrmed by the results in the following section). Evanescent ﬁeld illumination. Bright particles with intensities above a pre-determined threshold value were identiﬁed in each image. 2. 2. This characteristic allows easy detection of only particles that are close to the channel surface. ﬂood) illumination. Such background noise is attributed to the light emitting from the out-of-focus particles in the bulk of the ﬂuid and such images are common in micro-PIV measurements but lead to poor cross-correlations during PIV analysis.

Fluid Velocity Observation Range Glass Cover Slip Figure 2. For this reason we . illumination intensity varies exponentially with distance from the wall (as shown in Eq. Ovryn [71] developed a method to determine the three-dimensional position of a spherical particle.5: Schematic of near-wall particles moving near the surface illustrating the observation range. Thus. As the particle moves farther from the wall. representing a particle in contact with the channel surface. However in the evanescent ﬁeld. the intensity threshold chosen sets an upper bound on the observation range which is diﬀerent from the penetration depth of the evanescent ﬁeld. tracking the particles motion in the z -axis (normal to the surface) is not easy. Although tracking the particle displacements in the x -y plane (parallel to the surface) was straightforward. The exact size of the observation range was not known in these experiments and this uncertainty turned out to be the major source of uncertainty in these experiments and is discussed later on.4: Particle images of diﬀerent illumination methods: near-wall TIRFM image. 2. based on resolving the spatial variations in the scattering pattern. and hence into a region of lower illumination intensity.13 Figure 2. and consequently it is not easy to directly quantitatively associate the ﬂuorescent scattering of a particle in a non-uniform illumination ﬁeld with the particle’s distance from the wall. the emitted intensity also falls.2).

There is no reason why this should not be possible in the future. one would expect that the particle motion would be purely driven by thermal ﬂuctuations. A threshold displacement was imposed to detect error vectors. 74]. Figure 2. was used to compute the local diﬀusion coeﬃcient. The width of the particle displacement distribution. (2. ˙ did not attempt to track the particle’s motion normal to the surface.5) 2 . Indeed. which were deﬁned as displacements larger than deemed reasonable. Particles were matched between images using a custom particle tracking algorithm and displacement vectors were calculated from the displacements of particle centers.6: Distribution of particle velocity vectors of 200-nm particles with γ = 469 sec−1 .1 Cross-stream Velocity Analysis Analysis of the displacements of particles in the cross-stream direction was used as to check the consistency of the experiment results. the total number of validated displacement vectors ranged from 700 to 1500. we found that the distributions of spanwise velocities had a Gaussian distribution with mean and skewness close to zero. These large displacement vectors usually result from matching two diﬀerent particles mistakenly. 73. The Brownian motion is particularly strong due to the particle’s small size. Using the geometric scale and the applied pulse separation. in the absence of any mean ﬂow. At each testing condition. a velocity vector can be calculated from each displacement vector. σ. In this direction. D: σ 2 ∆t D= . and allowed us to locate the particle center coordinates with sub-pixel resolution. a two-dimensional Gaussian curve ﬁt closely approximates the Lommel function. Because the particles are known to be spherical with diameter standard deviation less than 5%.6 shows an example of a collection of velocity vectors obtained for a single shear rate.3.14 140 120 Streamwise veocity (μm/sec) 100 80 60 40 20 0 20 40 100 50 0 50 100 Cross-stream velocity (μm/sec) Figure 2. 2. The intensities of pixels surrounding the peak intensity were ﬁtted to a two-dimensional Gaussian curve [72.

7.6) 6πη where D0 is the Stokes-Einstein diﬀusion coeﬃcient. found by projecting the velocity distributions onto the mean ﬂow direction. we ﬁnd it to be 110 nm for the 200-nm particles and 165 nm for the 300-nm particles. x Radius (cm3/sec) 2. Unfortunately. Firstly.7: Cross-stream Brownian motion of particles in an inﬁnite medium and near wall (experiment). However. This is consistent with the high intensity threshold chosen which deﬁnes a small observation range. is independent of particle radius. The diﬀusion coeﬃcient is scaled by the particle radius. a more precise estimate is not available for this data. and η is the ﬂuid viscosity. The dashed line denotes particle diﬀusion in an inﬁnite medium calculated on the basis of the Stokes-Einstein relation. ♦. the measured values for D are approximately 30% that of the bulk diﬀusion expected. Coeff. Several features are worth noting. the location of the peak of the distribution increases with increasing shear rate. the measured spanwise diﬀusion coeﬃcients are independent of the streamwise shear rate and the diﬀusion coeﬃcient. 2. and the dotted lines represent scaled particle diﬀusion in an inﬁnite medium calculated based on the Stokes-Einstein relation: kB T D0 · r = . 38]. and Fig.7 shows the cross-stream diﬀusion coeﬃcient obtained for 200-nm (solid symbol) and 300-nm (open symbol) particles at a variety of diﬀerent streamwise shear rates over both hydrophilic and hydrophobic surfaces.5 1 0. 2. r. This is conﬁrmation of the presence of hindered diﬀusion of particles near a solid surface [37.5 x 10 0 0 500 1000 1500 2000 Shear rate (1/sec) 2500 Figure 2. T is the medium temperature.5 2 1. as indicated by the dotted line in Fig. 2.8 shows an example of the distribution of the streamwise velocities. .15 13 Diff. (2. kB is the Boltzmann constant. If we use the observed value of D with the theory for hindered diﬀusion [37. As expected. Solid symbol represents 200-nm particles and open symbol represents 300-nm particles ( . deﬁned as the distance between the particle center and the wall. hydrophilic surface. when appropriately scaled.2 Streamwise Velocity Analysis Figure 2. 38] to calculate the ”apparent particle distance” from the wall. hydrophobic surface).3. as one would expect. since we did not carefully monitor the observation range.

leading to the observed broadening of the velocity distribution for the streamwise velocity. including the current TIRV integrates through the observation range and thus samples particle motion from a range of shear planes over which the mean velocity changes. One would expect that the 300-nm particles would sample shear planes at higher local velocities than those sampled by 200-nm particles. for a ﬁxed observation range. and there are no discernible diﬀerences between the hydrophilic and hydrophobic surfaces and.15 at the low shear rate (barely noticeable) to a clearly observable positive value of 0.02 234 (1/sec) 1172 (1/sec) 2344 (1/sec) PDF 0. and thus the average velocities . In this case the most-probable velocity is quite diﬀerent from the average velocity. Thus.16 0. a particle is more likely to move upwards (and thus experience a higher local velocity) than to move downwards (and experience a lower local velocity). The lack of any diﬀerences between the mean velocities obtained for 200-nm and 300-nm particles is more troubling. Here. is the observation that the distribution widens with increasing shear rate. and that the skewness clearly shifts from 0. between the 200.85 (a stronger positive tail) at the highest shear rate presented. The velocities fall on a straight line through the origin. the true velocity distribution for tracer particles has a Gaussian shape with a mean equal to the ﬂow velocity at that plane. Less expected.8: Experimentally-measured distribution of streamwise velocities of 200-nm diameter particles over a range of shear rates. due to the presence of the wall. we note that. the error bars depict the standard deviation about the mean.01 0 200 0 200 400 600 Velocity ( μm/sec) 800 Figure 2. The reason for the observed increase in the distribution width and skewness can be explained in terms of the observation range from which particle motions are recorded. However. more interestingly. A similar argument can be used to explain the increasing skewness at higher shear rates. At each shear plane. Thus.and 300-nm diameter particles. raising a fundamental question about the deﬁnition of the actual ﬂuid velocity in terms of the observed particle velocity distribution.9 shows the variation of the mean velocities as a function of shear rate. and in contrast to the distributions for the spanwise velocities. higher velocity ﬂuctuations are more probable than lower ones in the vicinity near the wall (a similar argument is used to explain positive skewness in the streamwise velocity distribution in a turbulent wall-bounded ﬂow). any micro-PTV or PIV system. the range of mean velocities sampled increases as the shear rate increases. Figure 2. and standard deviation determined by the temperature and particle size.

if present. we ﬁnd that the average. this suggests that the slip length. is likely no more than 10 nm. including uncertainty in the measurement of the illumination observation range.150 nm. If we use a Navier representation for the slip velocity. our lack of quantitative knowledge about the evanescent wave penetration depth (which probably varied from experiment to experiment) and the observation range makes a more precise estimate for the slip length impossible at this time. us = l∗ γ. The drift velocities measured can result from two eﬀects: (i) the ﬁnite thickness of the observation range and (ii) the possible existence of a slip velocity at the surface. hydrophilic surface. representing this combination of both the penetration depth and the slip length. and other forces on the particles (e.9: Apparent particle velocity vs.g.9 is approximately 100-nm. should be larger for the larger tracer particles. 200-nm particle. At the present. 200-nm particle.8) The slope of the data in Fig. 300-nm particle. However. or ”apparent slip” velocity is u = (l∗ + δ) γ. we note that a slip length of order 1000 nm (as proposed by Tretheway . Given that the observation range is estimated to be approximately 100 . . (where ˙ ∗ is the slip length) and compute the average velocity in the mean depth of the observation range. [25] for these low shear rates. If we assume a constant shear very near the surface. with the appropriate characterization and consistent control of the observation range. particle motions in addition to pure translation (such as rolling motion). hydrophilic surface. ˙ (2. colloidal). We can assess the relative contributions of these eﬀects using a very simple theoretical model. there are several factors that are not yet well understood that could contribute to this counter-intuitive observation. l δ. we can write the local velocity proﬁle as: u (y) = us + γy. . this measurement will be possible and such experiments are currently underway. Finally.7) where us is the slip velocity. hydrophilic surface).17 400 Apparent velocity( μm/sec) 300 200 100 0 0 500 1000 1500 2000 Shear rate (1/sec) 2500 Figure 2. hydrophilic surface. consistent with the results of Choi et al. shear rate (♦. However. The fact that this is not observed remains a somewhat puzzling result and one that needs to be resolved in future measurements. ¯ ˙ (2. ◦. 300-nm particle. 2.

At each time step. as it would predict apparent slip velocities at least an order of magnitude larger than observed. For the Brownian motion parallel to the wall.000 particles were uniformly distributed between r and δ. To emulate the experiment. by the method of reﬂection [37. After 1000 time steps. the assumed upper bound of the observation range. At the beginning of the simulation. is such that D⊥ = D0 4 sinh α 3 ∞ n=1 n (n + 1) (2n − 1) (2n + 3) −1 (2. + 1. For the Brownian motion normal to the wall [36]. is such that [37] D 9 =1 − D0 16 45 − 256 h r h r −1 + −4 1 8 h r h r −3 1 − 16 −5 +O h r −6 (2.10) . 37. in a no-slip steady-state Couette ﬂow between parallel inﬁnite plates separated by a distance h. r. plate separation distance.18 and Meinhart [30]. 38]. ﬂow shear rate and the total time (1000 time steps) were chosen to be equal to measurement conditions.9) .3 Comparisons with Numerical Simulations The experimental results were compared with a numerical simulation of near-wall Brownian motion in shear ﬂow. 38] for (z − r)/r < 1. D⊥ . 38] for (z − r)/r > 1. the modiﬁed diﬀusion constant. Other eﬀects such as particle rotation. The motivation for this was to generate an intuitive model with which to help understand the experimental results. particles that remained within the observation range were counted and their displacements from their initial positions were calculated to obtain a particle displacement distribution. D . and Zhu and Granick [64]) is completely unsupported by these data.325 ln which is the asymptotic solution [37. and D =− D0 ln 2 ln h−r r 2 h−r r − 0.11) − 4. The Brownian motion was modiﬁed to account for the hindered diﬀusion both parallel and perpendicular to the wall [36. 2 sinh (2n + 1) α + (2n + 1) sinh 2α −1 4 sinh2 n + 1 α − (2n + 1)2 sinh2 α 2 where D0 is the Stokes-Einstein diﬀusion coeﬃcient. the modiﬁed diﬀusion constant. particle radii. and the assumed observation range was chosen to be 100 . similar to that obtained in the physical experiments. . 2. and would be independent of any reasonable estimate for the observation range.9543 h−r r .591 (2. This simple two-dimensional numerical model was developed to simulate the Brownian motion of particles with radius. each particle was moved by a linear combination of the mean shear ﬂow (evaluated at the particle’s geometric center) and Brownian motion (sampled from a normal distribution with a zero mean and a standard deviation √ of 2D∆t). the experimental channel depth.175 nm from the wall. etc were not considered at this time. 10.3. α = cosh−1 (z/r) and z is the distance between the geometrical center of a particle and the wall.

Nevertheless. 2. and that future experiments should pay more attention to this important issue.19 0. as a function of shear rate. . Only a few particles needed to be treated with these heuristic boundary conditions. and this result adds weight to our suspicion that the observation range in the experiments were not consistent.015 PDF 0. Problems can arise when the simulated particle is predicted to pass through the solid surface during the ﬁnite time step. The ﬁrst condition applied a specular reﬂection.9).01 0. and it was found that the two models gave almost indistinguishable results. quantitative. Unlike the experimental results in Fig. the similarities between the two ﬁgures are striking.005 0 200 0 200 400 600 Velocity (μm/sec) 800 Figure 2. there is a clear diﬀerence in the estimated velocity using diﬀerent particle size in Fig. while Fig. 2. As discussed earlier this diﬀerence due to particle size is to be expected for a ﬁxed observation range. The second condition emulated near-wall lubrication condition and simply allowed the particle to remain at the wall until Brownian motion perpendicular to the wall transported it back into the bulk ﬂow. denoted as error bars. but present) skewness of the distributions as the shear rate increases. In addition.11. one or more time steps later. Figure 2. with less than 1% statistical diﬀerence in the mean and standard deviation of the resultant particle distributions.10: Streamwise velocity distribution of 200-nm particles determined from Monte Carlo simulation at observation depth = 175 nm. the choice of observation range for the computation has not yet been optimized to match the simulation results with those of the experiments. 2. standard deviation and (less obvious. In the present simulation two diﬀerent wall boundary conditions were tested to deal with this situation. 2. comparisons with the experimental results (Fig.11 shows the variation of the mean velocities and their standard deviations.10 shows the streamwise velocity distributions of 200-nm particles at various shear rates. The rather simplistic nature of the simulation is such that one should not make direct. in which particle was simply reﬂected oﬀ the wall and back into the ﬂow.9 which did not show any diﬀerence in measuring velocity using diﬀerent particle size. showing similar increases in the mean.02 234 (1/sec) 1172 (1/sec) 2344 (1/sec) 0.8 and 2.

For this reason.11: Streamwise apparent velocity predicted by simulation ( . is of order 10 nm or less. ◦. and is limited by the same constraints . and comparable to ”standard” microPIV techniques. we were not able to measure vertical particle motion and our current resolution of the slip length measurement is limited such that we can only state that a slip length. smaller seed particles can move closer to the channel surface than larger particles. etc [70]. the technique also promises the ability to use intensity information to obtain wall-normal displacements as well as precise estimates for the slip velocity at the surface. Both changes will allow direct measurements of ﬂow velocities that are closer to the channel surface. the penetration depth of evanescent ﬁeld can be decreased. First. 2. 300-nm particles) at the observation depth of 175 nm. 200-nm particles. The present implementation did not (unfortunately) control with suﬃcient accuracy or consistency the characteristics of the evanescent wave penetration depth which is very dependent on the incident beam angle. diﬀraction-limited imaging of sub-micron particles. However. we have demonstrated the ability to measure both velocity distributions and mean velocities in the plane parallel to the surface. The accuracy of the TIRV system can still be improved by several means that are subject to future investigation. The determination of velocities in the streamwise and spanwise directions is extremely accurate.20 500 Apparent velocity (μm/sec) 400 300 200 100 0 0 500 1000 1500 2000 Shear rate (sec 1 ) 2500 Figure 2. where slip might contribute more signiﬁcantly to the local ﬂow velocity. by using a shorter illumination wavelength. TIRV images have very low background noise that allows accurate PIV and PTV measurements of ﬂow velocities within a few hundred nanometers of the surface. although they also suﬀer from higher Brownian diﬀusion and so the particle drop-out will increase. the estimate for the slip length is limited only by the accuracy with which we can measure the observation range and so we expect to be able to make measurements with uncertainties less than 5 nm in the near future. However.4 CONCLUDING REMARKS We have demonstrated that Total Internal Reﬂection Velocimetry (TIRV) can be a very powerful technique for the study of near-wall ﬂows in microﬂuidic systems. By using sub-micron seed particles. Secondly. if present. .the accuracy of particle centroid location.

[51]. the rate at which ions leak from the glass into solution). including non-Gaussian Brownian motion (due to the ﬁnite thickness of the observation range) and hindered diﬀusion due to near-wall lubrication eﬀects. thermal noise and electrostatic eﬀects (both the bead and the surface have surface charges). A full treatment of these issues is beyond the scope of the current paper. tracking each particle independently and then computing statistics from the individual particle motions might yield a more accurate view of the near-wall velocity ﬁeld. a second is the possibility of particlewall colloidal interactions and the relative roles of gravity. There are also eﬀects other than the translational hydrodynamic drag that can contribute to the particle motion such that the velocity measurements might be compromised. and most importantly. ionic strength (and for pure water such as used in these experiments. This is an area that has been studied by a number of researchers. Crocker and Grier [75] and Behrens and Grier [76] who have identiﬁed colloidal forces that are highly dependant on bead diameter. One is the possibility of particle rotation. . the experimental techniques described here to can be used in further studies of such phenomena. Perhaps the most important consequence of this is that techniques that treat ensembles of particles (such as PIV which looks at the collective motion of particles in an interrogation region. For this reason. surface charge. and indeed.21 Finally. the technique does raise fundamental questions regarding the use of ”passive” tracer particles to estimate the velocity ﬁeld in microﬂuidic systems. including Flicker et al. and often averages cross-correlations before peak detection) might be suspect close to walls due to particle interference eﬀects which cannot be neglected and where the particle motion is not represented by Gaussian statistics (and hence the average particle velocity is diﬀerent from the most probably particle velocity). Our results reveal several features of particle motion in the near vicinity of the surface.

27. 64]. 28. 31].Chapter 3 Paper 2: Direct measurement of slip velocities using three-dimensional total internal reﬂection velocimetry The existence and magnitude of slip velocities between deionized water and a smooth glass surface is studied experimentally. 27. slip velocity is inferred from other ﬂow quantities. 32. alternative techniques such as micro-particle image velocimetry (PIV) have resulted in direct measurements of near-surface ﬂuid velocity using tracer particles [30. For water ﬂowing over a hydrophilic surface. Issues associated with the experimental technique and the interpretation of results are also discussed. 26. 78. Although the direct measurements have a strong appeal. Although there is considerable disagreement regarding the existence of slip over a hydrophilic surface. 30. while the exact mechanism is not yet understood (for a review of this topic. Molecular dynamics simulations.1 INTRODUCTION The century-old assumption of the no-slip boundary condition between a liquid and a solid has been challenged by recent experimental results and molecular dynamic simulations and has been the subject of many recent investigations exploring ﬂows over both wetting and non-wetting surfaces. but increases slightly as the shear rate increases. In indirect measurements. suggest small slip lengths. 33]. The experiments have been conducted under various direct and indirect measurement techniques with varying accuracy and uncertainty. 64]. In contrast. ranging from micrometers [20. on the other hand. Experimental studies have reported a wide range of slip lengths. 31]. hundreds of nanometers [29. 77. to tens of nanometers or smaller (including no-slip) [25. 23. with the slip length reaching a maximum of 96 nm at a shear rate of 1800 s−1 . Surface hydrophobicity is observed to induce a small slip velocity. 24. there are two major drawbacks inher- 22 . 28. 3. the measurements are in agreement with previous experiments and indicate that slip. 79]. such as the relationship between ﬂow rate and pressure drop [25] or the measurement of the forces required to move a pair of crossed cylindrical surfaces separated by a thin ﬁlm of the test ﬂuid [26. Sub-micron ﬂuorescent particles are suspended in water and imaged using Total Internal Reﬂection Velocimetry (TIRV). is minimal at low shear rates. if present. mostly less than 100 nm [22. see [7]). it is generally believed that surface hydrophobicity aids slip.

In summary. (3. an evanescent ﬁeld can be created near a solid-liquid interface where total internal reﬂection occurs. 63. which is typically of the order of 0. respectively. 47. 3. (3.g. I. as illustrated in ﬁgure 4.2) 2 4π where λ0 is the wavelength of the incident light. 56. A second problem is that the size of measurement volume along the optical axis for ﬂood-illuminated microPIV techniques is deﬁned by the focal depth of the optical system.1) where I0 is the intensity at the interface and p is known as the evanescent wave penetration depth. Total internal reﬂection ﬂuorescence microscopy (TIRFM) has long been used by biologists to study near-surface dynamics [65. The ﬁrst is that the velocity is determined from the motion of a collection of particles in an interrogation area (IA) and. micro-PIV would still be insuﬃcient to provide an aﬃrmative conclusion if the true slip length is below 100 nm. [29] measured slip velocity of hexadecane over a sapphire substrate using TIRFM and ﬂuorescence recovery after photobleaching. Zettner & Yoda [56] combined micro-PIV and TIRFM to study near-surface Couette ﬂow while Pit et al. but were unable to make a conclusive determination of the size or character of any slip lengths due to diﬃculties in the determination the location of tracer particles within the narrow evanescent illumination region. in order to obtain a reasonable estimate of the velocity.2. 44. By measuring the intensity of tracer particles’ ﬂuorescence. One attractive approach that solves both of these problems is the use of Total Internal Reﬂection Velocimetry (TIRV) [80] which uses total internal reﬂection of an incident laser pulse to generate a highly localized illumination of the surface ﬂow. which characterizes the length scale of the evanescent ﬁeld. can be calculated from λ0 2 2 −1 p= n1 sin θ − n2 2 .23 ent to conventional micro-PIV. 67]. The ﬁeld intensity. 40.1. Although Joseph & Tabeling [31] reported a slip length measurement with 100-nm resolution. z. and in conjunction with a statistical model for the optical and hydrodynamic behaviour of small particles near a surface. 31].1 THEORETICAL CONSIDERATIONS Total Internal Reﬂection Microscopy The evanescent ﬁeld and its application to ﬂuorescence microscopy has been thoroughly documented in literature [e. The present manuscript reports on experiments in which the TIRV technique has been substantially improved to the point that quantitative statements can be made regarding the nature of slip velocities over hydrophilic and hydrophobic surfaces.5 to 1 micron [30. Hence the determination of phenomena which might measure a few nanometers is very diﬃcult to resolve. The penetration depth.2 3. we are able to track their motion within a narrow region above the solid surface and to compare that motion to the motion predicted for diﬀerent levels of boundary slip. 80]. . 66. and relies on tracking the motion of single tracer particles rather than the collective particle motion that is used in PIV. We ﬁrst reported on the TIRV technique in the context of slip velocities for near-wall microﬂows [80]. the IA must be measuring several hundred nanometers in size [30]. away from the two-medium interface by I(z) = I0 e−z/p . θ is the beam incident angle and n1 and n2 are the indices of refraction of the solid and liquid. decays exponentially with distance.

The intensity decay length can be obtained experimentally by statistically measuring intensities of particles as a function of particles’ distances away from the substrate.24 Figure 3. (3. including statistical variations in illumination intensity. and d is an intensity decay length that need not be the same as the evanescent penetration depth. If we parameterize all of these variations by an “eﬀective emission radius”. of a particle in an evanescent ﬁeld is I e (r. quantum eﬃciency of the imaging system and. Kihm et al. r. 3. I0 is the emitted intensity of a single particle with r = a located at h = a (ie. most importantly. [44] and the assumption that emission intensity of a ﬂuorescent particle is proportional to the number of ﬂuorophores within its volume. (3. a distribution in the physical size of the particles.3) and (3.1: Objective-based total internal reﬂection ﬂuorescence microscopy. [44] calculated the particles’ emission intensities as an exponential function of their distances to a substrate surface. Based on the calculation of Kihm et al. the emission intensity. that the intensity of ﬂuorescence emission from a large number of nominally identical particles can vary due to a variety of factors. Through experience we have found. we can model the particle’s probability density function (PDF) of its eﬀective emission radius with a Gaussian distribution P (r) = P0 exp − r a −1 2 σr 2 .3) where a is the mean eﬀective emission radius of the batch. touching the substrate surface).4) where h is the distance from the particle’s centre to the substrate surface at which total internal e reﬂection occurs. however. h) = r a 3 e I0 e−(h−a)/d . I e . σr is the characteristic variation (standard deviation) and P0 is a normalization constant. (3.2.4).5) P (I . h) = α exp − 2 σr . Combining (3. one gets the joint PDF of the emitted intensity and a particle’s distance to the substrate as 2 Ie 3 (h−a)/d − 1 e I0 e e .2 Emission Intensity of Fluorescent Particles For spherical tracer particles with a uniform volumetric ﬂuorophore distribution in an evanescent ﬁeld.

For a given imaging range of h1 < h < h2 . the transitions become more blurred. The e normalized intensity in the horizontal axis is deﬁned as I e /I0 .5 1 1.2). When an ensemble of tracer particles are imaged. with the brightest particles located at the surface (I e /I0 = 1) and the faintest particles e /I e = 0. and some larger particles close the wall contribute to the long tail at high observed intensities. however. However. The lower limit of this imaging range is h = a. they would certainly be located at a range of distances from the substrate surface. representing a particle touching the substrate surface.7) e . A sample plot of this distribution (3. such as an intensiﬁed CCD camera used in this study.8. I0 α . as the variation in particle radius at the outer edge of the evanescent ﬁeld (I 0 increases. the PDF of a tracer particle’s intensity is given by P (I e . h1 < h < h2 ) = h2 h1 P (I e .5) could also describe the particle position distribution within a normalized intensity range of e α < I e /I0 < β by β Ie e P (h. α < I e /I0 < β) = c(h) P (I e .6) is shown in ﬁgure 3. h)c(h) dh.05 σr = 0. while small particles close to the edge of the imaging e range are represented by the smooth transition close to I e /I0 = 0. h) d (3.25 1. The upper limit of the imaging range is determined by the sensitivity of the recording medium.2 for a range of values of σr .6) where c(h) is the concentration proﬁle of particles in the ﬂuid. we see that the particles in the deﬁned imaging range are sharply deﬁned in e intensity.5 0 0 0. When performing image analysis.2 1 PDF 0. Instead. Equation (3. and the calculation is performed with a normalized observation range of 0 < h/a < 3 and a normalized intensity decay length of d/a = 1.5 Figure 3. one can choose to identify and analyse only the particles within a certain desirable intensity range. For a low variation in eﬀective emission radius (σr small). ignoring particles that appear too bright or too dim.2: The emission intensity distribution of particles in a uniform concentration ﬁeld.5 σr = 0.1 σr = 0.15 σr = 0.5 Normalized Intensity 2 2. using particle intensity as a guide. one need not analyse all imaged particles. (3.

one can observe that the distribution has a long positive tail that gradually decays to zero at far away into the ﬂuid bulk.5 < I e /I0 < 1 in a uniform concentration ﬁeld. The most obvious feature of ﬁgure 3.3: The predicted position distribution of particles with 0.2. is given by U hS valid for large h/r.3 is that the distribution is nonuniform with the majority of particles contributing to this range of intensities coming from close to the substrate surface (< 250 nm).9) .7) is shown in ﬁgure 3. It is well known that shear and near-surface hydrodynamic eﬀects can cause a tracer particle to rotate and translate at a velocity lower than the local velocity of the ﬂuid in the same shear plane [12. These observations reinforce the fact that a particle’s intensity cannot be monotonically related to its distance to the solid surface. In addition. in a shear ﬂow with local shear rate. (3.2 ln h r 1− 5 16 h r −3 . [38] proposed that a particle’s translational velocity.18. we actually measure the velocity of small spheres near the surface. and U hS 0. and it is critical to recognize the diﬀerences between these two quantities. S. An example of this position distribution (3. 3.7431 0.8) −1 .5 < I e /I0 < 1.3 for a normalized intensity e range of 0. and attention should be given to any intensity-based quantitative analysis by recognizing the non-uniform position distribution and the contribution of particles far away from wall. a large particle far away (for example.26 8 x 10 −3 6 PDF 4 2 0 100 150 200 250 300 Particle Center Distance to Wall (nm) 350 e Figure 3.6376 − 0. a = 100 nm. d = 181 nm and σr = 0.3 Near-Surface Shear Flow Although we are interested in determining the velocity of a pure ﬂuid near a solid surface. Because of the large particle eﬀective radius variation in this example. > 300 nm) can exhibit in the same the same ﬂuorescence intensity as that of smaller particles close to the substrate surface. (3. In this prediction. Goldman et al. 38]. U .

c(h) is assumed to be uniform. a. calculated for the same imaging range. signiﬁcantly lower than that of pure ﬂuid velocity when the imaging range is very close to the substrate surface. which is a good approximation near a surface. α < I e /I0 < β) dh.4. of a large ensemble particles chosen from a normalized intensity range of e /I e < β and located in an imaging range of h < h < h is given by the average of the local α<I 0 1 2 velocity integrated over the imaging range: ¯ U= 1 h2 − h1 h2 h1 e U (h. S (h)) P (h.27 1 0.11) is based on a no-slip condition at the ﬂuid/solid interface.6 0.5 0.072332 ln h −1 r 2 (3. [38]: U hS r exp 0.5 4 Figure 3. [60] proposed a cubic approximation to numerical values presented by Goldman et al. U . and failure to recognize this eﬀect can lead to misinterpretation of the measured data and underestimation of slip lengths. (3.10) .54756 ln h +0. In the ¯ computation of U .11) ¯ ¯ This average apparent velocity.5 2 2. This diﬀerence must be incorporated into the data analysis. valid for small h/r.4: The ratio of statistical apparent velocity of particles and mean ﬂuid velocity under no ¯ slip in an imaging range of h1 < h < h2 .5 3.8 ¯ U ¯ V 0.4 1 1. at the solid boundary. of the pure ﬂuid. If there exist a slip velocity. V is computed with linear ﬂuid velocity proﬁle. Uslip . which is non-dimensionalized by particle radius.9 0. Pierres et al.68902 + 0. V . Although there exists no analytical approximation for intermediate values of h/r. U .0037644 ln h −1 r h −1 r 3 + 0.7 0. It should be noted that (3. ¯ The apparent velocity. The ratio of the two is shown in ﬁgure 3. from which we see that the average apparent velocity of particles is. not surprisingly. can be compared to the mean velocity.5 h2/r 3 h1/r = 1 h1/r = 1. the apparent velocity of the same ensemble .

28 of particles would be ¯ ¯ ¯ Uapp = Uslip + U = δSw + U . a long tubing (> 1 m long) was used to connect .3. capable of recording 1360-pixels-by-1036pixels 12-bit images. 250 ± 1 µm wide and 15 mm long. This volume of air acted as a pressure shock absorber to damp out the oscillatory forcing of the syringe pump screw. These microspheres have a peak absorption wavelength of 542 nm and emit a red light at 612 nm. Fluorescent particles were illuminated with an objective-based TIRFM method. The dimensions of the test channels were 50 ± 1 µm deep.35%). The roughness of the test surface was measured using an atomic force microscope prior to bonding. making relation of particle center distance from the solid wall and their ﬂuorescent intensities less reliable. To maintain steady pumping motions of the Harvard Apparatus stepper motor. 81]. 5nsec laser pulses (Quantel Twins Q-Switched Double Pulse Nd:YAG Laser) were directed through a Nikon PL Apo NA 1.45 100X TIRF oil immersion objective at an angle that created total internal reﬂection at a glass-water interface. Sw . Under 100X magniﬁcation.7 µm (calculated based on [70]). smaller particles do not contain enough ﬂuorophores to provide signiﬁcant signals with a 5-nsec laser illumination.1 EXPERIMENTAL PROCEDURES Materials and Setup A schematic of the image acquisition system is shown in ﬁgure 3.12) where the slip velocity is characterized as the product of the slip length. on the other hand. Test channels were fabricated using a polydimethylsiloxane (PDMS) (Dow Corning Sylgard 184) molding technique [69] and bonded onto polished glass wafers.3 3. In addition. thus illuminating the near-surface region of water with an evanescent ﬁeld (ﬁgure 4.47 nm and 0. 200-nm particles do not diﬀuse too far during the inter-frame time. Detailed coating procedures can be found in [80].3 nm in the ﬂow channel and the diﬀraction-limited spot size is 19. Fluorescent images of near-surface particles were projected onto a Q-Imaging Intensiﬁed Retiga CCD camera (ICCD). Secondly. (3. A TTL pulse generator (Berkeley Nucleonics Model 555) was used to synchronize laser pulses and image acquisitions. Lastly. To create hydrophilic microchannels. the pre-bonding PDMS surface was exposed to an oxygen plasma and immediately immersed in deionized-water after bonding to a glass wafer.04% volume fraction were used as tracer particles in this experiment. smaller size ﬂuorescent particles have much larger size variation. each image pixel corresponds to 64.5. we purposely introduced a large volume of air between the piston and the ﬂuid in the syringe. Monodisperse Fluorescent Polystyrene Microspheres (Duke Scientiﬁc) with diameters of 200 nm (± 5%) suspended in puriﬁed water (Fluka) at 0. There are three reasons that 200-nm diameter particles were selected as probes in this experiment. The energy of each illuminating laser pulse was recorded simultaneously with each image acquisition and this was used to adjust the resultant images and thus account for pulse-topulse variations in illumination intensity. 3. A Harvard Apparatus 22 syringe pump was used to maintain particle solution ﬂow rates. as detailed in [80]. Hydrophobic channels. and the wall shear rate. The hydrophilic and hydrophobic surfaces had an RMS surface roughness of 0. First. A pair of 532-nm.1). with diﬀusion out of imaging range being our major concern. It has been reported that water has a contact angle of 120 degrees with a similarly prepared OTS-coating [30. δ. ranging from 1 to 10 µL/min (±0. were fabricated by bonding untreated PDMS channels onto octadecyltrichorosilane(OTS)-coated glass wafers.35 nm respectively.

the test channel was ﬁlled with rhodamine-B solution. Although this is theoretically feasible. the syringe and the channel inlet.45 Objective lens Mirror Dichroic mirror and Barrier filter Convex lens Computer 1360 x 1036 x 12 bit Polarizing Beamsplitter NI_DAQ Pulse generator Nd-YAG laser 532 nm 532 nm. an experimental method was devised to obtain a ratiometric relation between particle emission intensity and its distance to the glass surface. This procedure has been reported to signiﬁcantly eliminate nanobubble formation [83]. At each distance to the surface. and subsequently ﬁtted to a two-dimensional Gaussian function to ﬁnd their centre intensities. Once all necessary images of particle motion were captured. It has been suggested that nanobubbles and a gas bubble layer on hydrophobic surfaces could be alternative sources of apparent slip [7. NA = 1. The process was repeated .4-nm precision stage (MadCity Nano-OP25). which were translated perpendicularly to the glass substrate in the evanescent ﬁeld with a 0.5: Image acquisition system. in practice. 1200 images were captured at each ﬂow rate. Particle ﬂow motion was observed to be very steady under this setup. 34. Thus. successful use of this technique requires precise knowledge of the illumination beam incident angle and a solution of Maxwell’s equation for an evanescent ﬁeld in a three media system (glass. 5 nsec pulse 2 . [44] used a ratiometric ﬂuorescence intensity to track particle motions three-dimensionally. Kihm et al. 82]. The pixel values of the imaged particles were then averaged. We attached individual ﬂuorescent particles to ﬁne tips of glass micropipettes. Prior to each experiment. which can be diﬃcult to express explicitly. water and polystyrene).29 PDMS channel Syringe pump 100X. Images of the rhodamine-B solution were subsequently captured under the same evanescent illumination.5 ms separation Half-wave plate Convex Lens 10 micron pinhole Convex Lens Pulse Energy Meter ICCD Power Attenuator Figure 3. the ﬂuid was degassed by placing the solution in vacuum for at least 30 minutes. 30 images of the attached particles were captured. It is intuitive to assume that one can infer the location of a particle in the evanescent illumination ﬁeld based on the ﬂuorescence intensity. as well as in quiescent ﬂuid. and averaged to obtain an image characterizing the spatial distribution of the illuminating laser beam.

several times with diﬀerent particles. they generally had a very low density and were usually placed at the edge of an image and far away from where the velocimetry measurements were performed. (nm) 150 200 Figure 3. very close to the evanescent penetration depth that we would predict based on the imaging lens. and the displacement was decomposed into streamwise and cross-stream components (for details of the tracking algorithm.6.2 Velocimetry Analysis The analysis of particle image pairs was performed using a custom particle-tracking program written in a MATLAB environment. every image was scaled by the measured laser illumination energy. λ. The particle intensities are shown in ﬁgure 3. along with a exponential ﬁt to the measured data: Ipeak = Ae−λ(h−r) + B.6 0.8 0.2 0 0 50 100 h−r. (3.3.30 Normalized Center Intensity 1 0. images of particles stuck on the glass substrate had to be removed from each image pair to prevent undesirable detection by the Particle Tracking Velocimetry (PTV) algorithm. 3. the signals due to stuck particles and background noise were removed by subtracting a reference image formed from the rolling average of 10 previous and 10 subsequent image pairs.13) where A. The ﬁtted curve predicts an intensity decay depth of 181 nm. The particle seeding density was low enough such .6: Fluorescent particle intensity as a function of its distance to the glass surface. is 181 nm.4 0. Prior to velocimetry analysis. B and λ are constants determined by a least-squares ﬁt. wavelength and refractive indices of the system. The particles used here are 200 nm in diameter. Velocimetry analysis started with ﬁnding the positions and peak intensities of all particles via threshold-identiﬁcation and Gaussian ﬁtting of the intensities of the pixels surrounding the peak. see [80]). Subsequently each particle’s displacement was obtained with a limited-range nearest-neighbor matching. The solid line is a least-square exponential ﬁt to the data whose decay length. To account for laser pulse energy ﬂuctuation. Although the presence of these stuck particles could distort the velocity ﬁeld. For each image.

400 nm.6). 3.2 Hindered Diﬀusion Near-surface tracer particles are known to exhibit anisotropic hindered diﬀusion due to hydrodynamic eﬀects. in quiescent ﬂuid).31 2 1. assuming an imaging range of 100 . Intensities of the “trackable” particles were converted to a normalized intensity ratio obtained by dividing the raw intensity counts by the average of all the stuck particles’ initial intensity counts. 3.5 1 1. The accompanying solid line is the theoretical prediction (3. particles within a desired normalized intensity range were selected for each ﬂow rate and their mean streamwise velocity was deﬁned as the apparent velocity of the ensemble.15.4. Finally.7 shows the distribution of particle intensities recorded during a typical data acquisition (in this case.6) for an imaging range of 100 to 400 nm and a 15% intensity statistical variation with a uniform concentration distribution of particles. For the hindered diﬀusion analysis.5 PDF 1 0.5 0 Intensity Ratio (Ie/Ie) 2 Figure 3. The good agreement between the observed and predicted intensity variation conﬁrms our calibration results and the statistical theory of the observed particle intensities discussed earlier. The solid line represents the theoretical prediction (3. and the hindered diﬀusion coeﬃcient in the direction parallel to the substrate surface .5 0 0 0. that this tracking was unambiguous.7: Observed ﬂuorescent particle intensity distribution and its probability density function (PDF). the same analysis steps were followed except that diﬀusion coeﬃcients of particles in quiescent ﬂuid were obtained from the variance of displacements instead of velocities. and an eﬀective emission radius variation of σr = 0.4 3.4.1 RESULTS AND DISCUSSION Validation of Intensity Calibration Curve Figure 3.

+ 1. Physically.4 0. D is [37] D 9 =1− D0 16 h r −1 + 1 8 h r −3 − 45 256 h r −4 − 1 16 h r −5 +O h r −6 . and their asymmetric shapes show an increasing skewness as the shear rate increases. (3. This “Method of Reﬂection” approximation is generally valid for (h − r)/r > 1. Note that the streamwise velocity distributions widen as shear rate increases. For (h − r)/r < 1.15) − 4. D =− D0 ln 2 ln h−r r 2 h−r r − 0.8: Ratio of hindered diﬀusion coeﬃcients (Dexp ) for Brownian motion parallel to a surface.8. The results further improve our conﬁdence in the overall experimental method and subsequent analysis.6 0.32 1 0. The increasing distribution width and skewness at high shear rates are both results of sampling particle displacements from an imaging range with ﬁnite thickness [80]. Goldman et al.325 ln The combination of our particle-tracking algorithm and the intensity calibration curve was applied to analyse near-surface particle Brownian motion parallel to the glass substrate. 3.8 Dexp/D0 0.591 (3.14) and shown in ﬁgure 3.4. including the fall in the eﬀective diﬀusion coeﬃcient close to the surface.14) where D0 is the Stokes-Einstein diﬀusivity of a spherical particle in the ﬂuid bulk. The results are compared to the Methods of Reﬂection calculation (3. The experimental data shows reasonably good agreement with the theory.5 2 Figure 3.2 0 0 Data 1 Data 2 Method of Reflection 0.9543 h−r r . at higher shear rates.9 shows distributions of particle velocities at three diﬀerent shear rates.5 1 (h−a)/a 1. hence the increasing width of the . [38] proposed an asymptotic solution. the ﬁnite-thickness imaging range contains particles that are translated by a wider range of local velocities.3 Velocity Distributions of Particles Figure 3.

s 2D0 ∆t (3. It can be observed that small Peclet numbers are associated with greater distribution widths while the distributions collapse onto a single skewed distribution at high Peclet numbers. Here the Peclet number is deﬁned as the ratio of the shear-induced displacement.9.02 S = 183 sec−1 S = 732 sec−1 0. during the interframe time period. the shear-induced eﬀects in all velocity distributions in ﬁgure 3. the eﬀect of shear ﬂow on particle motion increases and when P e > 3. P e. Data include measurements of ﬂow over a hydrophobic surface. V (3. ∆t.17) Because V is shear-dependent only. Thus the distribution exhibits a more pronounced positive skewness at the higher shear rates. particle motions are completely shear-dominant.10 are scaled to equal magnitudes.005 0 −200 0 200 400 600 800 Particle Velocity (µm/sec) 1000 Figure 3. As the Peclet number increases.10. L. It should be noted that the overlapping . In addition. is scaled by V − V ˜ V = . s.9: Distribution of observed particle streamwise velocities under various shear rates. The explanation is the following: at low Peclet numbers the distributions widths scale inversely to shear. V . because the particles are conﬁned by the solid wall. suggesting a diﬀusion dominance and thus the large widths of the velocity distributions are due to Brownian motion. they are more likely to move away from the wall and into a faster moving shear plane. apparent velocity distributions.015 PDF S = 1465 sec−1 0. the relatively contributions of velocities from shear ﬂow and Brownian motion can be characterized by the Peclet number. Pe = L V ∆t =√ . The scaled velocity distributions are shown in ﬁgure 3.16) ˜ where V is the scaled streamwise particle velocity and V is the mean value of each velocity distribution. At each shear rate. causing the distributions to overlap.01 0. The eﬀect of shear with a ﬁnite-thickness imaging range can be characterized if the streamwise particle velocity in ﬁgure 3.33 0. to the diﬀusive displacement.

the intensity distribution of all “trackable” particles were compared to the theoretical prediction (3.52 0.10: Distribution of observed particle streamwise velocities after scaling the velocities distributions in ﬁgure 3.11)).20. these velocities were compared to the experimental apparent velocities (mean values of the streamwise velocity distribution) of particles from the same normalized intensity range to extract experimental slip velocities and slip lengths.28 Pe = 4. 3.1 and ﬁgure 3.12).5 −1 −0.4 Measurements of Apparent Slip Velocities For each ﬂow case.5 Figure 3. Subsequently. A quantitative comparison of the two cases shows a slip length attributed to surface hydrophobicity ranging from -7 nm at low . we calculated the theoretical apparent velocities of a particle ensemble.12 show the experimental and theoretical apparent velocities as a function of wall shear rate over hydrophilic and hydrophobic surfaces.34 1.12)).5 0 0.20 Pe = 1. Figures 3. with a more observable increasing trend of wall shear rate dependence at higher shear rates. 3.93 Pe = 3. on the other hand. The velocities are scaled according to (3.11 and 3.4. The dashed and dotted lines are the expected apparent velocities if one were to assume a 50-nm and a 100-nm slip length.6) to identify the unknown parameters such as h1 .5 1 PDF Pe = 1. With these parameters known.28 and 4. In the case of the hydrophilic surface (ﬁgure 3. In both ﬁgures.5 Scaled Particle Velocity 1 1. 732 and 1465 sec−1 in ﬁgure 3. which are absent in small Peclet number cases. the increasing distribution width and skewness at high shear rates are both eﬀects of shear.17). respectively.43 correspond to the shear rates of 183. h2 and σr through optimization. the solid lines represent the theoretical apparent velocities assuming zero slip (equation (3. suggests a larger slip length ranging from 37 to 96 nm. The data obtained for ﬂow over the hydrophobic surface (ﬁgure 3.5 0 −1.9.11).43 Pe = 5. These observations conﬁrm the explanation that in ﬁgure 3. chosen from a normalized intensity range. distributions have the same distribution width. respectively (calculated using (3. asymmetric shape and the same positive tail.4. the measured slip length ranges from 26 to 57 nm with a slightly increasing trend as wall shear rate increases. respectively.16 Pe = 4. P e of 1.7.12) and varying the slip length conditions. as demonstrated in section 3. by using equation (3.9.9.

35 700 Apparent Velocity (µm/sec) 600 500 400 300 200 100 0 0 500 1000 1500 Wall Shear Rate (1/sec) 2000 No Slip (Theoretical) Slip length = 50 nm Slip length = 100 nm Exp. [84]). shear rates to 54 nm at the highest tested shear rate.11 and 3.13). which could serve as the upper limit of imaging range uncertainty. There are three possible sources of measurement uncertainty in ﬁgure 3. If there is signiﬁcant slip at the wall. 64].12) do . One should note that the corrections due to shear-induced rotation (ﬁgures 3. The additional slip caused by surface hydrophobicity is in agreement with many experimental results [25. In addition. the shear rates could be slightly lowered than the reported values. 28.11: Experimental apparent velocity of particles in a shear ﬂow over a hydrophilic surface e (0. and its comparison to slopes of expected apparent velocities if there exists a 0. In all cases the 95% conﬁdence intervals are within ±3% of the reported mean velocity values. with an uncertainty of 20 nm taken into consideration. 26. The error bar of each experimental data point represents a 95% conﬁdence interval. our PTV algorithm is able to track particle displacements with high accuracy (< 0. Because wall shear rates are calculated based on microchannel dimensions and ﬂow rates which are controlled by the syringe pump. (b) the apparent velocities of particle ensembles and (c) the imaging range. we estimate that the uncertainty in the wall shear rates is less than 3%. 50 or 100-nm slip length.21 < I e /I0 < 0.12: determination of (a) the wall shear rate. 31]. the largest measured slip length still will not exceed 150 nm – much smaller than other experimental studies which reported slip lengths greater than a few hundred nanometers.11 and 3. 33.1 pixel. it should be noted that. with subpixel resolution of the particle centre detection. and thus the slip eﬀect on wall shear rate calculation can be safely neglected. data Figure 3. The determination of apparent velocities of particle ensembles also has extremely low uncertainly because central limit theorem constrains the statistical mean of a large sample (a few thousand trackings) to a very low uncertainty (< ±3% of the reported velocity values for 95% conﬁdence intervals).78). However. but is in sharp disagreement with others [30.6 where intensity measurements were performed in increments of 20 nm. However. The imaging range is determined statistically based on the particle intensity decay length obtained from ﬁgure 3. with an average value of 16 nm in between (ﬁgure 3. The largest source of uncertainty is the determination of the imaging range. the largest observed slip length is less than 1% of the channel height.

60 Additional Slip Length (nm) 40 20 0 −20 0 500 1000 1500 Wall Shear Rate (1/sec) 2000 Figure 3. and its comparison to slopes of expected apparent velocities if there exists a 0.12: Experimental apparent velocity of particles in a shear ﬂow over a hydrophobic surface e (0. The error bar of each experimental data point represents a 95% conﬁdence interval.36 600 Apparent Velocity (µm/sec) 500 400 300 200 100 0 0 500 1000 1500 Wall Shear Rate (1/sec) 2000 No Slip (Theoretical) Slip length = 50 nm Slip length = 100 nm Exp. 50 or 100-nm slip length.5 < I e /I0 < 1.0). . In all cases the 95% conﬁdence intervals are within ±3% of the reported mean velocity values. data Figure 3.13: The additional slip length due to surface hydrophobicity.

as a ﬁrst approximation. Because the slip length calculations in ﬁgure 3. Secondly. suggesting that our reported slip lengths are most likely the upper bound of the true slip length value. electrostatic repulsion can create a depletion layer near the substrate surface that eﬀectively shifts the imaging range.5 CONCLUDING REMARKS The results presented here represent direct measurements of local velocities in the near wall region of a ﬂuid-solid boundary. Lumma et al. however. based on the overall particle seeding density. calculations suggest that. 3. surface slip is unlikely to be an issue. we can qualitatively estimate its eﬀect.37 not account for the possibility of slip between the ﬂuid and the tracer particle. slip will reduce the shear-induced rotation of the particle. we can ignore this eﬀect. For our experimental setup. Nevertheless. recognizing the possibility of such depletion layer’s existence.9 µm for a pure water and glass combination. Perhaps a more accurate direct measurement of the true surface slip can be obtained if aqueous solutions of moderately high ionic strengths were used. In contrast. [51] experimentally measured the depletion layer thickness to be in the order of 10 to 30 nm. Lauga [35] reported that a streaming potential can induce electrophoretic motion of particles if particle surfaces are charged. because the tracer particles have relatively rough surfaces. Electrostatic interaction between tracer particles and surface could also aﬀect accuracy of velocimetry measurements [7]. Flicker et al. The slip length we measured with sub-nanometer surface roughness. and applying this theory to the current conditions results in an “apparent” slip length of at most 18 nm. [38] to include the eﬀect of surface slip. Granick et al. This is in close agreement with our experimentally-derived images. [33] suggested that the depletion layer thickness can be as large as 0. and we can conclude that the depletion layer thickness must be much smaller than our imaging range and thus eﬀects due to a depletion layer thickness of this magnitude would not be detectable with our current imaging technique. It should also be noted that Joseph & Tabeling [31]. Since these two mechanisms act in opposition to each other. It has also been suggested that electrokinetic eﬀects could signiﬁcantly aﬀect velocimetry measurements of suspended particles close to a surface. [34] and Lauga et al. Such a thickness seems unreasonably large as it is much bigger than the evanescent ﬁeld penetration depth and consequently few ﬂuorescent particles would be observed. hydrophobic coating and shear rates. Despite the relative simplicity of the experiment. Physically. reported slip length very close to the present results. agrees well with the surface roughness dependency reported by Zhu & Granick [26]. however.12 are based on the assumption that particle concentration is uniform near surface. and we are unaware of any work that extends the theory of Goldman et al.11 and 3. We found such a shift would result in higher theoretical apparent velocities of particle ensembles and therefore lower slip lengths for all shear rates. we believe that. If the tracer particles and the substrate surface are similarly charged. we re-analysed the theoretical curves in ﬁgure 3. However. Firstly. Slip between the ﬂuid and the tracer particle will modify the particle velocity in two ways.11 and 3. if the particles are uniformly distributed in the ﬂuid one should be able to see around 19 particles in a 26 µm-by-26 µm image ﬁeld. the reduced shear force will result in the particle velocity lagging the local ﬂuid velocity. [7] both pointed out that large surface roughness can signiﬁcantly decrease slip. The electrostatic and electrokinetic interactions are an interesting pair as their signiﬁcance decreases with increasing ionic strength of the test ﬂuid. several subtle issues . with ﬂow experiments conducted under similar surface roughness.12 by assuming an imaging range farther away from the substrate surface. a depletion layer could be a source of “apparent slip” if it is not recognized.

and that this might well reveal the reasons behind the range of reported apparent slip phenomena.38 need to be carefully addressed. . However. 31] that there is minimal slip over hydrophilic surfaces. the tracking in the wall-normal direction is currently limited to an accuracy of approximately 10% of the evanescent penetration depth (about 20 nm in the current case). we believe that a consensus is forming from more recent experiments that the slip eﬀect is not as extreme as some studies might have suggested. such as electrokinetics and nanobubbles. Although the present technique does allow for measurement of particle motions very close to the solid surface. measurement and interpretation of slip data in the nanoscale can be very tricky because other physical phenomena. Most notably. and the statistical variations in the eﬀective visibility of the seeding particles. As many authors have pointed out. might lead to observations of an “apparent slip” caused by other complicating factors. and if the imaging system noise can be reduced (both of which are technical improvements on the immediate horizon).12) over the range of shear rates tested. If particles with a higher degree of monodispersity can be reliably found. the eﬀects of the local shear on the dynamics of seeding particles. there is no possibility that the ﬂow exhibits a slip length more than 150 nm (ﬁgure 3. it does suﬀer from some limitations and there is room for improvement. we believe that the technique can be used to track particles with an order of magnitude improvement in accuracy. including the spatial non-uniformity of the illumination region. but small boundary slip. All of these suggest that close attention must be to paid to documenting the experimental conditions. and that hydrophobic surfaces do appear to introduce a discernable. even with the current levels of uncertainty. While the debate of slip versus no-slip will likely continue in the foreseeable future. The current experiment conﬁrms previous measurements in our own group [25] as well as some other recent measurements [26.

By conducting a threedimensional TIRV (3D-TIRV) experiment. and p is the evanescent wave 39 . A total internal reﬂection velocimetry (TIRV) technique was recently reported to be an eﬀective method in measuring liquid velocities in the region of less than 300 nm from solid surfaces [80]. e I e (z) = I0 e−h/p .Chapter 4 Paper 3: Direct measurement of slip length in electrolyte solutions The emergence of microﬂuidics over the past decade has brought out increased research interests in liquid boundary slip. 28. 33]. reported that slip length can be obtained within a 20-nm uncertainty [85]. 21. Advancements in ﬂow measurement techniques have resulted in many recent experiments reporting aqueous slip length with a wide range of values and various degrees of dependency on applied shear rate. 35].1). They reported a small but non-negligible slip length for de-ionized aqueous solutions in shear ﬂows over both hydrophilic and hydrophobic surfaces. as an attempt to answer these open questions. Huang et al.1) e where h is the distance between the particle center and the solid phase. In this letter. 31. slip length measurement of ionic aqueous solutions using TIRV is presented and compared to the previous results of Huang et al. and relies on tracking motions of individual tracer particles to determine ﬂuid velocity vectors in the planes parallel to a solid surface (as demonstrated in ﬁgure 4. [85]. exhibits the same exponentially decaying characteristic as the evanescent ﬁeld energy does. 32. Subsequently slip velocities and slip length can be inferred from the measured apparent velocity vectors by applying a statistical model for optical and hydrodynamic behaviors of small particles near a solid/liquid interface. was presented by Huang et al. 25. 26. I e . However. including a proof of concept and a discussion of its subtleties. namely. its emission intensity. The TIRV technique uses total internal reﬂection of an incident laser beam to generate a highly localized illumination of the near-boundary liquid phase. surface hydrophobicity and surface smoothness [20. A detailed description of the 3D-TIRV theoretical work. When a ﬂuorescent particle of radius a is illuminated by an evanescent ﬁeld of incident wavelength λ0 (a < λ0 ). A brief summary is presented in this letter to facilitate the readers’ understanding and resultant discussion. which for centuries has been regarded as negligible. The exponentially decaying evanescent ﬁeld leads to determination of tracer particles’ positions in the direction normal to the solid surface based on their ﬂuorescent intensities. I0 is the emission intensity of the particle when it is in contact with the solid phase (h = a). some questions remained as to whether electrostatic and/or electrokinetic forces acting on the tracer particles could lead to false slip observation [7. (4. 30.

Because tracer particles are used to probe near-surface shear ﬂow. the shear-induced lift under the presented experimental conditions is insigniﬁcant. a variety of factors. most importantly. However. and the local ﬂuid shear rate. or eﬀective emission radius. penetration depth. Thus. including statistical variations in illumination intensity. of the particle distance to the solid surface and emitted ﬂuorescent intensity can be obtained.3) h 2 − h1 h 1 Because equation (4. (4. quantum eﬃciency of the imaging system and. . However. non-uniformity of the particle sizes. U . h. α < Ie < β) dh. ¯ The ensemble-averaged velocity. it is important to recognize that shear and near-surface hydrodynamic eﬀects can cause a tracer particle to rotate and translate at a velocity. which characterizes the length scale of the evanescent ﬁeld. P (h.2) 2 4π where n1 and n2 are the indices of refraction of the solid boundary and liquid. Uslip . a. I e ). the corrected particle translation velocity does not account for the possibility of slip between the ﬂuid and the tracer particle. assurance is needed that the particle ensemble uniformly samples all shear layers. It should be noted that in the presented analysis. and thus any calculation based on U represents a no-slip case. 60]. The penetration depth. Factors that determine the particle translation velocity include particle radius. and thus alleviating this concern (see Appendix B). based on the theory presented by Cherukat & McLaughlin [87]. can be calculated by h2 1 ¯ U= U (h. a. can be calculated from λ0 2 2 −1 p= n1 sin θ − n2 2 . can lead to variations in the observed ﬂuorescent intensities of an ensemble of nominally identical particles. of a large number of uniformly distributed particles emitting in an intensity range of α < I e < β and located in an imaging range of h1 < h < h2 . 38.1: Objective-based total internal reﬂection velocimetry (TIRV) system. particle distance to the solid surface. respectively. lower than the velocity of the local ﬂuid element in the same shear plane [12. S (h). with which a joint probability density function (PDF). if there exists a slip velocity. It has been suggested that shear-induced lift can be a source of particle migration away from the solid wall [86].40 Figure 4. Therefore corrections need to be made when one convert ﬂuid velocities into particle velocities. U . S (h)) P (h. If near-wall velocities of a pure ﬂuid are to be measured by tracking motions of tracer particles. a statistical analysis is carried out by characterizing these variations through a single parameter r. (4.3) is based on a no-slip boundary condition.

This procedure has been reported to signiﬁcantly eliminate nanobubble formation [83]. Prior to each experiment. γw .45 100X TIRF oil immersion objective at an angle that created total internal reﬂection at a glass-water interface.4) where Uslip is characterized as the product of the slip length. 34. The hydrophilic and hydrophobic glass surfaces had an RMS surface roughness of 0.005-0.35 nm respectively. respectively. the ﬂuid was degassed by placing the solution in vacuum for at least 30 minutes. with special attention paid to removing pulsations and maintaining steady pumping motions. one slip length can be obtained for each wall shear rate. ˙ (4. but is in sharp disagreement with some others [30. These microspheres have a peak absorption wavelength of 542 nm and emit at 612 nm.41 at the liquid/solid substrate interface. the same particle ensemble will exhibit an apparent velocity of ¯ ¯ ¯ Uapp = Uslip + U = δ γw + U . Finally. Hydrophilic and hydrophobic microchannels were created by oxygen plasma treatment of the PDMS mold and by bonding untreated PDMS channels onto octadecyltrichorosilane(OTS)-coated glass wafers. Lauga [35] suggested that for an aqueous solution with 1 . The dimensions of the test channels were 50 ± 1 µm deep. Monodispersed Fluorescent Polystyrene Microspheres (Duke Scientiﬁc) with diameters of 100 (±10%) and 200 nm (±5%) suspended in puriﬁed water (Fluka) at 0. Detailed description and schematics of the experimental setup have been presented in [85].2 shows the measured slip lengths of aqueous solutions under various experimental parameters. 26. With U ˙ calculated by using equation (4. Slip lengths were then obtained based on equation (4. In summary. thus illuminating the near-surface region of water with an evanescent ﬁeld (ﬁgure 4. Test channels were fabricated using a polydimethylsiloxane (PDMS) (Dow Corning Sylgard 184) molding technique [69] and bonded onto polished glass wafers. The ﬁrst observation to be made is that all measurements report slip lengths of approximately 100 nm or less.1). The additional slip caused by surface hydrophobicity is in agreement with many experimental results [25. velocimetry analysis started with ﬁnding the positions and peak intensities of all particles via threshold-identiﬁcation and Gaussian ﬁtting of the intensities of the pixels surrounding the peak. The analysis of particle image pairs was performed using a custom particle-tracking algorithm. Slip on a hydrophobic surface appears to be slightly higher than on a hydrophilic surface. 33]. It ˙ ¯app can be experimentally measured by ﬁnding an ensemble-averaged velocity should be noted that U ¯ of “trackable” tracer particles while γw is computed from ﬂow rate and channel geometry. The ﬂows were driven by a Harvard Apparatus 22 syringe pump. 250 ± 1 µm wide and 15 mm long. These results further conﬁrm previously reported measurements [25. A quantitative comparison of all measurements shows that the slip length attributed to surface hydrophobicity averages to 22 nm at the tested shear rates. particles within a desired intensity range were selected for each ﬂow rate and their mean streamwise velocity was deﬁned as the apparent velocity of the ensemble and compared to theoretical no-slip values. however. Figure 4. Fluorescent images of near-surface particles were captured by a Q-Imaging Intensiﬁed Retiga CCD camera (ICCD). is expected to decrease with increasing ionic strength of test ﬂuids.04% volume fraction were used as tracer particles in this experiment. 85] that there is minimal slip over smooth solid surfaces. Approximately 1000 images were captured at each ﬂow rate. 28. and the wall shear rate. 31]. δ. Electrokinetic eﬀects [35] and electrostatic repulsion between tracer particles and glass surface [7] have both been proposed as sources that might cause an apparent slip and could aﬀect the accuracy of slip velocity measurements.3).47 nm and 0. Subsequently each particle’s displacement was obtained with a limited-range nearestneighbor matching. A continuous-wave 514-nm Argon-ion laser beam (Coherent) was directed through a Nikon PL Apo NA 1. 82]. which could be an alternative source of apparent slip [7. 31. Their signiﬁcance. 26.4).

Hydrophilic 200−nm. Still. 31]. Hydrophilic” and “200nm. To assess this. variations in aqueous ionic concentration do not change measured slip lengths signiﬁcantly. a TIRV system equipped with a very sensitive high-speed camera would be needed for measurements at high shear rates. as the conducted measurements span only one order of magnitude of shear rates. DI−water. Zhu & Granick [26]. but are consequences of true boundary slip. As shown in ﬁgure 4. DI−water. 0. Hydrophobic 200−nm. Hydrophobic” have been previously reported by Huang et al. 1mM NaCl.1mM NaCl. DI-water.2. The uncertainty of each slip length measurement (not drawn for plot clarity) is less than 20 nm. mM NaCl concentration. 29. The error bar on each data point represents a 95% conﬁdence interval of each ensemble calculation. It is physically plausible that the shear dependence of slip length is nonlinear and the shear eﬀect is signiﬁcant only at higher shear rates. Neto et al. estimated based on penetration depth calibration and particle radius variation [85]. Hydrophobic 50 0 0 500 1000 1500 Wall Shear Rate (1/sec) 2000 Figure 4.2: Measured slip lengths of aqueous solutions. [25] all tested over larger ranges of shear rates (> 2 orders of magnitude) and reported shear-dependent slip lengths. [27] and Choi et al. Hydrophobic 100−nm. the apparent slip length would become sub-molecular. Hydrophobic 200−nm. Data of “200-nm. DI−water. DI-water. This observation suggests that the measured slip lengths are most likely not due to ionic eﬀects. this result does not suggest that slip length is independent of shear rates. This observation agrees with experimental studies conducted under similar ranges of moderate shear rates [28. Another important observation is that the slip lengths do not vary signiﬁcantly over the tested range of shear rates.42 Apparent Slip Length (nm) 150 100 200−nm. .

Chapter 5 Paper 4: Direct measurement of anisotropic near-wall hindered diﬀusion using total internal reﬂection velocimetry By applying the three-dimensional total internal reﬂection velocimetry (3D-TIRV) technique to freely suspended micron-sized ﬂuorescent particles. Inside a ﬂuid bulk the diﬀusivity of an isolated particle follows the Stokes-Einstein relation. In the presence of a nearby solid boundary. a particle would experience an increased. [37] for gap-size-to-radius ratio much less than one. 42]. total internal reﬂection ﬂuorescence microscopy (TIRFM) [43. many experimental studies have been conducted to observe hindered diffusion and to verify the correction factors. which is the ratio of ﬂuid thermal energy to the particle’s hydrodynamic mobility. and hindered diﬀusion anisotropicity is simultaneously observed in all data sets. The displacement measurements reveal that the hindered diﬀusion coeﬃcients are in close agreement with the theoretical values predicted by the asymptotic solutions of Brenner [36] and Goldman et al.and nano-particles in engineering research (eg. particle imaging velocimetry) and biotechnology (eg. 40. Demonstrated experimental techniques include evanescent light-scattering [39. simultaneous three-dimensional measurements of the anisotropic diﬀusivity could not be 43 . however. 5. [37] were the ﬁrst to developed drag force correction factors for near-wall spheres under no inertial eﬀects and a no-slip boundary condition. Brenner [36] and Goldman et al. These correction factors have since evolved into theories of hindered diﬀusion [88].1 INTRODUCTION Advancement in colloidal sciences have lead to many applications of micro. We demonstrate that the three-dimensional tracking technique of TIRV used for nanoparticles can be adopted into 3D displacement measurements of freely suspended 1. At these length scales Brownian motions are signiﬁcant and understanding these thermal agitations are essential in making practical use of these tiny particles. Following these works. In most of the above mentioned studies. anisotropic drag which hinders its mobility. drug delivery).5-µm radius particles. 44] and combined optical tweezers and digital video microscopy [41]. we aim to simultaneously observe the threedimensional anisotropic hindered diﬀusion for gap-size-to-radius ratio much less than one.

its Brownian motion is hindered due to an increase in hydrodynamic drag. [37] oﬀered an asymptotic solution. [41].2 THEORY OF HINDERED DIFFUSION When an isolated particle is at the vicinity of a solid boundary. and the gap size between the particle and the wall. using a regression method.9543 h a . In addition. deﬁned by h/a 5.2).3 EXPERIMENTAL PROCEDURES To experimentally verify equations (5. diﬀusion of micron-sized ﬂuorescent particles in an evanescent ﬁeld was tracked with digital imaging microscopy. in measuring motions of near-wall nanoparticles [89]. no study has demonstrated the anisotropic hindered diﬀusion for h/a 1 with a simultaneous three-dimensional measurement as studies of Banerjee & Kihm and Lin et al. Later Bevan & Prieve [39]. who reported anisotropic diﬀusivities that only partially agree with the theories.1) is a close approximation to Brenner’s inﬁnite series solution. who demonstrated that the anisotropic hindered diﬀusion could extend far away from the wall. Based on our literature survey. + 1. ﬂuorescent intensity of the particles can be used to infer the instantaneous separation distance between the particle and the two-media interface. Another exception is a study reported by Lin et al. The presence of the solid wall also breaks the symmetry of particle dynamics. a. have been demonstrated by Huang et al. In the theories of Brenner and Goldman et al. resulting in anisotropic Brownian motion. reported that β⊥ ≡ D⊥ 6h2 + 2ah ≈ 2 D0 6h + 9ah + 2a2 (5. β . an exact analytical solution was never found. h. They proposed analytical solutions of the hindered mobility that are vastly diﬀerent for h/a 1 and for h/a 1. a. β ≡ D =− D0 ln 2 ln h a 2 h a − 0. 5. both attempted to measure hindered diﬀusion at h/a 1. β⊥ . probably due an inaccurate accounting of particle positions. TIRV allows particle centers to be identiﬁed on the captured ﬂuorescent images. 90]. the hindered mobility of a near-wall particle is a function of the particle’s radius. as commonly done in traditional TIRFM experiments [44. and consequently particle motions can be tracked via the displacements of particle centers. Unlike evanescent light-scattering experiment of non-ﬂuorescent particles.44 conducted due to experimental limitations. . termed 3D-TIRV. Brenner [36] successfully solved the lubrication equation of particle motion normal to the solid wall and proposed an inﬁnite series solution of the drag correction factor. One exception is a ratiometric-TIRFM measurement conducted by Banerjee & Kihm [43].325 ln 1.2) − 4. In this paper we present our experimental study aimed to validate the anisotropic mobility correction coeﬃcients for h/a 1 through a direct measurement of hindered diﬀusion using three-dimensional total internal reﬂection velocimetry (3D-TIRV). (5. Instead. For the diﬀusivity correction factor in the direction parallel to the solid wall. and the gap size between the particle and the solid wall. He reported that the correction factor is a function of the particle radius. The technique.591 for particles very close to the wall. h.1) and (5. Goldman et al.

The water phase was an aqueous solution consisted of 10mM NaCl and individual 1.5-µm radius ﬂuorescent polystyrene particles were attached to polished conical tips of thin graphite rods. Spherotec Inc. Our 3D-TIRV setup was created on an inverted epi-ﬂuorescent microscope (Nikon TE-2000).51) Figure 5.4-nm precision translation stage.9◦ . Still.33) ~ penetration depth θ glass (n = 1. especially in determining the relationship between the particle/wall gap size and the particle’s peak ﬂuorescent intensity. To do so. collimated 514-nm Argon-ion laser beam was directed through a Nikon PL Apo NA 1. a calibration experiment was necessary to verify its validity for 1. 200 µL of the solution was injected into a closed reservoir formed by a piece of carved polydimethylsiloxane (PDMS) sandwiched between glass coverslips. This method has been previously demonstrated in TIRV with nanoparticles. and recorded at a 10-Hz frequency. ensured the isolated-particle assumption of the theories was met. total internal reﬂection occurs at the glass/water interface. or 32 nm.02% volume fraction. By mounting the assembly to a 0.5µm-radius (±5%) ﬂuorescent polystyrene particles (refractive index 1. greater than 61. A red ﬂuorescent microparticle suspended in water is placed in a green evanescent ﬁeld created within the focal depth of a high numerical aperture microscopy objective. At the illumination beam incident angle. Subsequently TIRV imaging of hindered particle Brownian motions was performed at one of the glass/solution interface. the ﬂuorescent particles were traversed through the evanescent ﬁeld and their ﬂuorescent images were digitally captured at various distances to the glass surface. A particle’s 3D position was determined through threshold-identiﬁcation and Gaussian ﬁtting of the intensities of the pixels surrounding the peak.1: Schematic of TIRV. 2000 to 2500 sample images were captured for each experiment for reliable statistics. Before each measurement the solution was sonicated in intervals of 30 seconds for 10 minutes to disperse coagulated particles. individual 1.45 100X TIRF oil immersion objective at an angle that created total internal reﬂection at a glass/water interface.2.5-µm particles. and thus low particle number density. Because the particle radius is much larger than the evanescent penetration depth. Overall.5 pixels. We also found that the precision of center identiﬁcation was approximately 0.) suspended at 0. A continuous-wave. A collimated laser beam through the objective is used as the illumination light source. The result of this calibration is shown in ﬁgure 5.59. θ. The low volume fraction.45 z x water (n = 1. the evanescent energy illuminates only the lower portion of the encapsulated ﬂuorophores. . The close agreement between particle intensity’s exponential decay length and the evanescent ﬁeld penetration depth suggests that particle-glass gap size can be reliably inferred from the particle peak intensity. For image acquisition. The ﬂuorescent images of the particles were projected onto a Q-Imaging Intensiﬁed Retiga CCD camera (ICCD).

The hindered diﬀusion coeﬃcient in the direction parallel to glass surface.4 RESULTS AND DISCUSSION Shown in ﬁgure 5.2: Gaussian-ﬁtted peak intensities. diﬀusion coeﬃcient of the same 1. The laser incident angle is 64◦ and the resulting evanescent ﬁeld penetration depth is 148 nm.3 are hindered diﬀusion correction factors measured by 3D-TIRV. of 1. and represents ensemble average.5-µm radius ﬂuorescent particles in evanescent ﬁeld. I0 is the ﬁtted intensity at h = 0. 5. Finally. hindered diﬀusion coeﬃcients from a Brownian dynamics simulation [89] are also plotted for comparison. These results are compared to the asymptotic solution of Goldman et . With an exponential decay length of 142 nm.5-µm particles were measured in the ﬂuid bulk.6 I/I0 0. ∆t is the time between consecutive image acquisitions (= 100 millisecond). In addition to experimental results. D⊥ . Similarly. Each data point represents the particle peak intensity averaged over 10 images.2 0 0 Particle 1 Particle 2 Particle 3 Exp. the hindered diﬀusion coeﬃcient in the direction normal to glass surface.4) where ∆z is the particle displacement normal to the glass surface. All data series exhibit an exponential decay tendency versus gap size. to obtain the hindered diﬀusion correction factors. taken at 0 to 275 nm away from the glass surface. fit (d = 142 nm) 50 100 150 200 Gap size.8 0.4 0. using regular ﬂuorescent digital microscopy. while the length of the error bar spans two standard deviations. β and β⊥ .46 1 0. the best ﬁt of the intensity data shows close agreement to the penetration depth. D . particle displacements were calculated between consecutive frames.3) where ∆R is the averaged radial displacement of particles. Once positions of all imaged particles were determined. was calculated from the equation ∆R 2 = πD ∆t (5. h (nm) 250 300 Figure 5. I. was calculated from (∆z)2 − ∆z 2 = 2D⊥ ∆t (5.

1 in the same h/a range.) DX (Exp. β ≡ Dx /D0 . Theoretically equation (5. (equation (5. “Exp.3 0. Each error bar represents the 95% conﬁdence interval of measurement.025.4 at h/a ≈ 1.) DZ (Sim. who conducted one-dimensional hindered diﬀusion measurement in the range h/a < 0.2) is more appropriate for the measured gap sizes of h/a 1 while the method of reﬂection solution is more accurate at h/a > 1.2) but signiﬁcantly deviate from the MOR solution.1 0 0 0.3: Hindered diﬀusion correction factor (Dx /D0 . demonstrating the anisotropicity of near-wall hindered diﬀusion.#1) DX (Exp.2 at h/a ≈ 0 to 0. Each data point is obtained from an ensemble of particles found within ±0.2)). the Bevan approximation and “Method of Reﬂection” solution. Bevan’s approximation (equation (5. The transition from the asymptotic solution to the method of reﬂection solution is demonstrated at h/a > 0. The correction factor in the direction parallel to glass surface.4 0.1 h/a GCB MOR Bevan DX (Sim. while the correction factor in the direction normal to glass surface.3.#2) 0.7 0.05 are very close to that predicted by equation (5.05 0. One of these forces is gravitational . A close agreement between the measured and the predicted β⊥ values at extremely small h/a has also been reported by Oetama & Walz [42]. Finally. respectively. we realize the importance of recognizing other acting physical forces that could lead to measurement inaccuracy.01 of the targeted gap size values.” represents experimental data while “Sim. As in most near-wall colloidal measurements.. increases from 0 to 0.” means data obtained from Brownian dynamics simulation.2 0. conﬁrming the validity of our measurement technique. It is observed that the measured β values at h/a < 0.5 D/D0 0.15 0.2 Figure 5. Dz /D0 ) vs. “MOR” and “Bevan” represent asymptotic solution of Goldman et al. β⊥ = Dz /D0 .1 where measured β⊥ is slight larger than the predicted values possibly due to insuﬃcient or slightly biased particle sampling.1 as the measured β values fall between the two solutions. increases from approximately 0. D0 is the diﬀusion coeﬃcient measured in the ﬂuid bulk while Dx = D and Dz = D⊥ .#1) DZ (Exp. the experimental data also agree well with the simulation results. The measured β⊥ agrees well with Bevan’s approximation.47 0. “GCB”. non-dimensional gap size between particles and glass surface (h/a). but nevertheless they are both plotted for a quantitative comparison.#2) DZ (Exp.6 0.05 < h/a < 0. conﬁrming the validity of the asymptotic solution at h/a 1. except at 0.1)) and a “Method of Reﬂection” (MOR) solution [37]. al.005 or ±0.

when the particle approaches the solid boundary. In the ﬂuid bulk of density ρf and dynamic viscosity µ. Zhu & Granick [26] concluded that apparent slip lengths are only a few nanometers if the rms surface roughness is 3.5 nm or larger. Besides hydrodynamic interaction. based on the theory of particle mobility presented by Vinogradova [93]. By adding 10 mM of NaCl to the solution. we found few particles came close to glass surface. electrostatic repulsion can also exist between the polystyrene particles and the glass surface as they both carry negative surface charges when immersed in aqueous solution [51]. this terminal settling velocity would be 245 nm/sec. Thus under the current experimental conditions. it is expected that the theories of Brenner and Goldman et al. Because the polystyrene microspheres used in the current hindered diﬀusion experiment are hydrophilic and have surface roughness of at least 10 nm [92]. First. slip of such magnitude would have an insigniﬁcant eﬀect on the particle mobility for the particle diameter and particle-wall gap size under consideration. Indeed when the same ﬂuorescent particles were suspended in de-ionized water and observed under evanescent wave imaging. However. if not subnanometer. However the length scale of electrostatic repulsion can be easily decreased by increasing the electrolyte concentration of the suspending aqueous solution.1). we decreased the electric double layer thickness surrounding the particles and the glass surface to a Debye length ∼ 3 nm. would under-estimate near-surface particle mobility and the hindered diﬀusion coeﬃcients. oﬀer insights into whether slip eﬀect should be taken into consideration. or equivalently a non-dimensional gap size of 0. for a particle/glass gap size of 10 nm and greater.5 nm during the imaging inter-frame time of 0. equivalent to a settling displacement of 24.3. At a ﬁrst glance. within the evanescent penetration depth the particles would settle for a distance of less 2.0016 for our measurement gap size of h/a < 0. van der Waals force scales with h−3 [91]. The hydrodynamic mobility correction factors proposed by Brenner and Goldman et al. ws . For a 1.1 seconds. h/δ 10.1 seconds.5-µm radius polystyrene particle of density 1050 kg/m3 . and is additionally veriﬁed by the agreement between experimental data and theoretical values shown in ﬁgure 5. Based on equation (5. Consequently. and thus signiﬁcantly reduced the eﬀect of electrostatic repulsion. If ﬂuid slip exists at the particle surfaces. Another colloidal force that could potentially aﬀect measurement accuracy is van der Waals force between the particles and the glass. its terminal velocity is expected to decrease with a correction factor identical to β⊥ for the same hydrodynamic reason of decreased mobility.002. the eﬀective slip length at particle surfaces. Therefore the no-slip assumption is considered valid in the current experiment. . assume a no-slip boundary condition at particle surfaces. δ. the terminal settling velocity. however. Several recent theoretical and experimental studies.5) ws = 9µ where g is the gravitational acceleration. making its eﬀective range even shorter than that of electrostatic repulsion. is expected to be of only a few nanometers in magnitude. or h/a ∼ 0. of a particle with radius a and density ρp is 2 (ρp − ρf ) ga2 .14. by conducting slip measurements of water ﬂowing over hydrophobic surfaces.45 nm in the inter-frame time of 0. it is perceivable that sedimentation could lead to bias in diﬀusion measurement normal to the glass boundary. (5. Therefore in the time scale of our Brownian motion measurements. However.48 pull or sedimentation of the particles. sedimentation can be considered as a negligible factor. Thus it is safe to assume that van der Waals force is also insigniﬁcant for the range of h/a under consideration.

5 SUMMARY A direct measurement of hindered diﬀusion was conducted with total internal reﬂection velocimetry. . and such correction shall be applied to not only diﬀusion but also other translational motion of particles where the drag force is of concern.49 5. We believe that this is the ﬁrst simultaneous three-dimensional measurement of hindered diﬀusion coeﬃcients for h/a 1. The results conﬁrm the increase of hydrodynamic drag when a particle approaches a solid boundary. The anisotropic characteristic of hindered diﬀusion is experimentally conﬁrmed and the correction factors are found to agree with the theories of Brenner and Goldman et al.

if the time interval between successive particle image acquisitions is long. 6. are found to be a potential source of measurement error for nano-PIV because of the rapid Brownian motion of nanoparticles.[55] and nano-scale [56] where size of tracer particles has also decreased from microns to nanometers. The combined eﬀect of the observations described above is that near-wall particle-based velocimetry measurement is not time-invariant. and the eﬀects of the wall presence and hindered diﬀusion on the measured apparent velocities are explored through Brownian dynamics simulations with diﬀusive time and particle radius as time and length scales. 85] or a method of statistical tracking [94]. In the past decade. an under-estimation of ﬂuid velocity can result from biased sampling of tracer particles very close to the wall. Its accuracy heavily relies on the assumption that tracer particles will accurately trace local ﬂuid velocities. Brownian motion of tracer particles can be quite signiﬁcant. This scaling method. a statistical analysis of the particle ensemble [80. resulting in an over-estimation of overall ﬂuid velocity. At these physical length scales. thus violating the assumption of particles travelling at velocities equal to that of the surrounding ﬂuids. Particle drop-in’s and drop-out’s. It is observed that the shear force dominates over diﬀusion at P e > 3. It is also found that if the time interval between successive particle image acquisitions is short. respectively. Still. however. However. Consequently. an ensemble correlation averaging technique [54]. conducting an accurate velocimetry experiment requires a good understanding and a careful treatment of Brownian motion via either a thorough error analysis [55]. making TIRV the more superior method in near-surface measurements. particle image velocimetry (PIV) has been extended to the micro. and asymmetric shape and width of apparent velocity distributions are attributed to the shear eﬀect.1 INTRODUCTION Colloidal particle-based image velocimetry has long been used as an experimental method in measuring ﬂuid velocity proﬁle and other physical quantities. a signiﬁcant portion of the tracer particles would sample planes of higher velocities. is available only for TIRV but not for nano-PIV.Chapter 6 Paper 5: Simulations of hindered diﬀusion in shear ﬂow and its implications for near-wall velocimetry The ensemble behaviors of near-surface particles in a shear ﬂow. 50 . the results found in the Brownian dynamics simulation oﬀer a way where the true ﬂuidic velocities can be inferred from particle apparent velocities through proper scaling.

both Dx and Dz would be equal to the Stoke-Einstein . its displacement between simulation time step i and step i + 1 with a step size δt is. In most cases. We then discuss the simulation results and their implications. (6. 42. The other approach is a Brownian dynamics (BD) simulation. 38] and experimentally [39. The usefulness of BD simulations has been demonstrated in studying the impact of hindered Brownian diﬀusion on the accuracy of nano-PIV [63]. Only a few researchers managed to turn the disadvantages into merits by proposing usage of the extent of hindering to reconstruct near-wall shear ﬂow velocity proﬁle [96] and to probe the no-slip boundary condition [97]. dz kB Θ 2Dz δt . which is to simulate motion of each particle in a large ensemble through a stochastic diﬀerential equation. kB is the Boltzmann constant and Θ is the ﬂuid temperature. 37. This is known as hindered diﬀusion and has been reported both theoretically [12. in their total internal reﬂection velocimetry (TIRV) experiment [80]. where (x . To study the ensemble behavior of hindered and non-hindered Brownian motions. [59] had taken the Fokker-Planck approach to study the hindered diﬀusion of particles in the direction normal to the wall and its eﬀect on the bias of velocimetry.1b) dDz Dz δt + Fz δt + N 0. on the colloidal particle deposition in a microchannel ﬂow [61]. which solves the momentum-space partial diﬀerential equations to obtain a time evolution of spatial conﬁguration function of the particle ensemble. both deterministic (such as ﬂuid ﬂow and sedimentation) and stochastic (such as Brownian motion) processes contribute to particle displacements. such a spatially dependent Brownian motion would lead to greater diﬃculties in accessing measurement uncertainties. Dx and Dz are the diﬀusion coeﬃcients in the directions parallel and normal to the solid surface.51 In the vicinity of a solid wall. Sadr et al. Details provided by this method are not only intuitive in understanding ensemble behavior but also bear a close resemblance to physical velocimetry experiments. respectively. In this paper the theories of near-wall particle dynamics will ﬁrst be presented and followed by a detailed description of the BD simulation algorithm. it would be of interest to examine how the relative strength of hindered diﬀusion and shear ﬂow leads to skewed near-wall apparent velocity distributions ﬁrst reported by Jin et al. xi+1 − xi = U δt + zi+1 − zi = dDx Dx δt + Fx δt + N 0. dx kB Θ 2Dx δt . 43.1 THEORIES AND COMPUTATIONS The Langevin Equation In Brownian dynamics simulation. One is the Fokker-Planck approach. Recently.2 6. For a particle in a shear ﬂow as shown in ﬁgure 6. time between image acquisitions and the accuracy of velocity measurements based on ensemble averages. In addition. particle displacements are computed based on a stochastic Langevin equation [58]. 95]. and on the accuracy of potential energy proﬁles determined via total internal reﬂection microscopy [62]. there are two equally appropriate approaches [58].1.2. a colloidal particle will undergo a “hindered” Brownian motion due to an lubricational increase of its hydrodynamic drag. 36. and the relationship between particle diﬀusion. 6. In this approach. What has yet to be examined is the eﬀect of hindered diﬀusion and the presence of the wall on the accuracy of velocimetry. z ) is the particle’s center position.1a) (6. In the ﬂuid bulk. and conclude with a summary and our thoughts on the accuracies of various velocimetry methods. The grand simulation then yields a spatial distribution of the particle ensemble after each time step. 41.

As it has been mentioned earlier. as the time scale. 2Dδt denotes the stochastic displacement of Brownian motion randomly sampled √ from a normal distribution with a zero mean and a standard deviation 2Dδt. respectively.1b) are non-dimensionalized by choosing the particle radius.1a) and (6. √ and N 0. diﬀusivity. dDx /dx = 0 in equation (6. a2 /D0 . The z -dependency of Dx and Dz is discussed in section 6.1: A schematic of the simulation geometry.3b) . A colloidal particle of radius a is freely suspended in a ﬂuid but near a solid boundary. The gravitation sinking force acting on the particles. Fg . Even though existence of slip has been reported [85].3. is thus the only external force in the z-direction and Fg = 4π 3 a ∆ρg. near-wall diﬀusion is anisotropic and hindered.1a) and (6.2. and g is the gravitational acceleration. Therefore equations (6. 2βz (Zi ) δT (6. and thus Dx < D0 and Dz < D0 . as the length scale and time required for the particle to diﬀuse a distance of one radius.3a) dβz dZ δT + G · βz Zi δT + N Zi 0. on the other hand. its presence would not alter the simulation results and is thus neglected. 2βx (Zi ) δT (6. 3 (6. D0 .and z-directions.52 a U S z’ z x x’ Fluid Solid Figure 6.1a). The ﬂuid is undergoing a shear ﬂow of shear rate S. It should be noted that because Dx is only a function of z . and thus the particle translates due to both ﬂuid ﬂow and its Brownian motion. In the current BD simulation scheme there exists no force in the x-direction and Fx = 0. Density mismatch between tracer particles and the suspending ﬂuid. A no-slip boundary condition is assumed at the ﬂuid/solid interface. The equations of motion (6.1b) become Xi+1 = Xi + F Zi · P e · Zi · δT + N and Zi+1 = Zi + 0.2) where ∆ρ is the density diﬀerence between the tracer particles and the suspending ﬂuid. Fx and Fz represent external forces acting on the particle in the x. leads to either sedimentation or ﬂoatation of the particles. a.

042 × 10−5 -0.2 and 6. ∆T . another important control parameter is the time between consecutive image acquisitions. where X ≡ x /a. P e. G.630 4630 G= −5.1: Sample values of the Peclet number. Pierres et al. D0 G≡ 4πa4 g∆ρ .54756 ln Z − 1 (6.2. Z ≡ z /a.5) 1− 5 Z 16 −3 . ∆t. (6. U .2 ln (Z − 1) (6. respectively and F Z ≡ U .00022 ∆t = 10 msec 2.2: Representative values of the non-dimensional time between consecutive image acquisition. and T ≡ D0 t/a2 are the non-dimensional x .1 msec 0.072332 ln Z − 1 + 0.0463 46. Some sample values of non-dimensional time between consecutive image acquisition.68902 + 0.6) 2 +0.22 0.022 0. and U ≡F Z zS 0.1. [60] proposed a cubic approximation to numerical values presented by Goldman et al.4630 463.4) for small Z . 38]. [38] proposed that the translational velocity. for 1-µm and 100-nm particles are shown in table 6. G.5042 a = 100 nm a = 1 µm Table 6.3 while Pe ≡ Sa2 .000022 ∆t = 1 msec 0. 6.0 103 sec−1 4. z and t.0046 4. of a particle with radius a in a shear ﬂow of a local shear rate S is given by U ≡F Z zS which is valid for large Z .0022 ∆t = 100 msec 22 0.022 Table 6.2. Although there exists no analytical approximation for intermediate values of Z . a = 100 nm a = 1 µm ∆t = 0.0037644 ln Z − 1 3 .630 101 sec−1 0. and sedimentation coeﬃcient.7431 0. characterizes the gravitational pull on the particles. In image-based velocimetry measurements. D0 βz Z ≡ Dz (z ) D0 as described in sections 6. and the sedimentation coeﬃcient.2. Goldman et al.2 Eﬀects of Shear on Particle Velocities It is well known that shear and near-surface hydrodynamic eﬀects can cause a tracer particle to rotate and translate at a velocity lower than the local ﬂuid velocity in the same shear plane [12.2 0. . in [38]: U ≡F Z zS 1 Z exp 0. zS βx Z ≡ Dx (z ) .53 S = 100 sec−1 P e = 0.2. P e. 3kB Θ The Peclet number. represents the relative strength of shear force and diﬀusion. Representative values of P e and G are shown in table 6. ∆T .30 102 sec−1 0.6376 − 0.

Like the particle translational velocity. Dx ≡ βx Z D0 =− 2 [ln (Z − 1) − 0.2.4 Implementation of Simulation Since the experiments are conducted using dilute suspensions. based on the theory presented by Cherukat & McLaughlin [87]. 2 sinh (2n + 1) α + (2n + 1) sinh 2α −1 4 sinh2 n + 1 α − (2n + 1)2 sinh2 α 2 where α = cosh−1 (Z ). and thus will be neglected (for details. where the particle would be in contact with the wall.3 Hindered Diﬀusion Near-wall tracer particles are known to exhibit anisotropic hindered Brownian motion due to hydrodynamic eﬀects. A boundary condition was needed in the event that a particle attempted to enter the solid wall during a simulation step. (6. Goldman et al.3a) and (6. Dx . the modiﬁed diﬀusion constant. .9543] .54 Because a particle’s translational velocity depends on the shear rate and the distance to the wall.and nano-particles in a low shear ﬂow regime.10) well approximates equation (6. For Z < 2. the smallest Z value a particle could have was Z = 1. it needs to be updated in equation (6. the dependence of these hindered diﬀusion coeﬃcients on Z requires them to be updated at every time step of the simulation. Because the solid wall was located at Z = 0. is such that [36] Dz ≡ βz Z D0 = 4 sinh α 3 ∞ n=1 n (n + 1) (2n − 1) (2n + 3) −1 (6. The simulation then progressed for a total of ∆T /δT steps as prescribed by equations (6. and their hindered diﬀusion coeﬃcient in the direction parallel to the solid surface. the BD simulations were conducted under an assumption of no particle-particle hydrodynamic interactions. [38] proposed an asymptotic solution.8) In the direction normal to the wall. [ln (Z − 1)]2 − 4. Z ) of the particle recorded after each time step. see Appendix B). It has also been suggested that shear-induced lift can be a source of particle migration away from the wall [86]. the shear-induced lift is insigniﬁcant for micro. Bevan & Prieve [39] reported that the equation βz Z = 6 (Z − 1)2 + 2 (Z − 1) 6 (Z − 1)2 + 9 (Z − 1) + 2 (6.1a) at every time step of the simulation. 6.3b).2. with F and β’s updated and the position (X . This “Method of Reﬂection” approximation is more accurate for Z > 2. is [37] Dx ≡ βx Z D0 =1− 9 Z 16 −1 + 1 Z 8 −3 − 45 Z 256 −4 − 1 Z 16 −5 +O Z −6 . Dz .591 (6.325 ln (Z − 1) + 1. a particle was situated at X = 0 and randomly placed in a pre-determined range of 1 < Z < 10. However. At the beginning of each simulation.9) .7) where D0 is the Stokes-Einstein diﬀusivity of an isolated spherical particle in the ﬂuid bulk.9) and is much less computationally intensive than the inﬁnite series. 6.

5-µm particles. Therefore δT was chosen to be 10−4 . on the other hand. the time step must be much greater than the particle relaxation time. 2D0 ∆t . Particles that start oﬀ farther away from the wall can diﬀuse a longer distance within a given amount of time. δT 1). as demonstrated by the wider displacement distribution widths. nano-PIV and TIRV as tracers. However. Finally. or the z-direction.1 RESULTS AND DISCUSSIONS Sedimentation Accurate particle velocimetry measurements require unbiased sampling of ﬂuid velocities by particle ensembles. these displacement PDF’s are more symmetric and collapse onto each other. mD0 /kB Θ. it is important to mention the selection of the size of the computational time step. Shown in ﬁgures 6. In both case the ﬁnal spatial distribution agrees with the Boltzmann distribution prediction [91]. 6. With the time step taken small enough. non-uniform spatial distribution after a transient period. with the presence of the wall hindered diﬀusion is expected to break the symmetry of the displacement PDF.001% of the simulated displacements required applications of the boundary condition.3 6. Secondly. 99] have studied the eﬃciencies of diﬀerent boundary conditions for BD simulations. It was also repeated for various values of parameters P e and G to study their eﬀects. it can be observed that the distribution started out uniformly.3. but do serve to validate our simulation. which has two physical constraints [58].4. which satisﬁes both constraints and was numerically eﬃcient. respectively. sampled after various times ∆T . With sedimentation being negligible for small particles.55 Peters & Barenbrug [98. The single particle simulation was then repeated 105 times to obtain a large ensemble. In the case of 1. as these particles are commonly used in micro-PIV. the use of the boundary condition was seldom triggered and less than 0.3. The displacement PDF’s of near-wall . These results are not surprising.2 Particle Displacement Due to Hindered Diﬀusion The ﬁrst observation made is the displacement probability density function (PDF) of hindered Brownian motion in the direction perpendicular to the wall. In addition. numerical accuracy requires that the time step must be short enough such that the diﬀusion coeﬃcients and their gradients are essentially constant during the time step (that is. δT .3 are BD simulations of particle distribution for 1.5-µm and 100-nm radius particles. where m is mass of one particle. It is well known that the one-dimensional displacement PDF of an isolated particle in the ﬂuid bulk is a Normal √ distribution N 0.2 and 6. First. 6. The initial positions of particles and the seeding of our random number generator were made identical for all runs of simulations to ensure that the diﬀerences in results found between runs were the consequences of simulation parameters only. A common bias of this sort is sedimentation of particles between image acquisitions.11) kB Θa2 for a > 100 nm. but evolves with time and eventually settle into a steady. and is demonstrated in ﬁgure 6. we concentrate on presenting results of sub-micron particle simulations. Here we chose a simple and yet eﬀective specular reﬂection to prevent a particle from entering the wall. The 100-nm particles. remain dispersed through the volume at all times. In nondimensional terms it is equivalent to mD0 2 δT ∼ O 10−6 (6.

56 (a) 1 0.2 0 1 2 3 4 5 Z (b) 2. . The particles are uniformly distributed in the volume (1 < Z < 10) at T = 0 and allowed to diﬀuse only within this volume. which is equivalent to a 1.2: Sedimentation of particles at G = −2. PDF stands for probability density function.5.8 PDF 0.5 ΔT=1 ΔT=2 ΔT=3 ΔT=5 Figure 6.5 1 0.5 0 1 2 3 4 5 Z 6 7 8 9 10 ΔT=5 ΔT=6 ΔT=7 ΔT=8 ΔT=9 Δ T = 10 Boltzmann Distribution 6 7 8 9 10 ΔT=0 Δ T = 0.5 2 PDF 1.4 0.6 0.5µm-radius polystyrene particle (density 1050 kg/m3 ) suspended in pure water.

12 0.5 T=1 T=2 T=3 T=5 9 10 Figure 6.06 0.06 0.04 1 2 3 4 5 Z 6 7 T=5 T=6 T=7 T=8 T=9 T = 10 Boltzmann Distribution 8 9 10 6 7 8 T=0 T = 0. which is equivalent to a 100nm-radius polystyrene particle (density 1050 kg/m3 ) suspended in pure water. .57 (a) 0. The particles are uniformly distributed in the volume (1 < Z < 10) and allowed to diﬀuse only within this volume.1 PDF 0.08 0.04 1 2 3 4 5 Z (b) 0.3: Sedimentation of particles at G = −5 × 10−5 .08 0.1 PDF 0.12 0.

After long periods of time when the particles are allowed to reach the wall through diﬀusion (∆T > 0.5. initially uniformly distributed within the imaging range. with the spatial distribution skewed toward the wall (Z = 0).3 Particle Drop-in’s and Drop-out’s The accuracy of velocimetry measurements relies on the ability to detect the same particles in consecutive image acquisitions. The particles. more particles would drop out with longer inter-acquisition time. The portion of the particles that are not present in the imaging range at the second image acquisition are said to have “dropped out”.1.5.5 0 −2 −1 0 Z − Z0 1 2 Figure 6. which is a good estimate for evanescent wave imaging using 100-nm radius particles.3. Further proof of the hindered diﬀusion eﬀect is shown in ﬁgure 6. on the other hand. which is a direct consequence of hindered diﬀusion. Suppose the imaging range of near-wall microscopy is 1 < Z < 5.58 2 Z0 = 1. One such situation is demonstrated in ﬁgure 6. Clearly. images of the dropping in particles at the second image acquisition would lead to additional errors . In PIV. many “outside” particles would have to “drop in” to take over the space.3). This is especially diﬃcult in near-wall microscopy measurements because near-wall sub-micron particles can diﬀuse away from the near-wall region quickly.4: Displacement distribution of small particles from various initial positions. 6. the skewness of the spatial PDF is even more pronounced. are signiﬁcantly skewed with a more pronounced tails in the positive values and are narrower. Such time-dependence of the particle spatial distribution could lead to time-dependent apparent velocity measurements and is further discussed in section 6.5 PDF Z0 = 2 Z0 = 6 Z0 = 11 1 Z0 = 51 Z0 = 101 0. leading to a high concentration of particles at the wall.6. For the overall concentration of the particles to remain uniform. This observation suggests that hindered diﬀusion could lead to a bias of measurements toward values obtained in the near-wall region. during which time no particle is able to reach the wall. Particles start to diﬀuse away from the initial position of Z = 2 as time evolves. All particles are allowed to diﬀuse for an identical time ∆T = 0. will start to leave the imaging range as time evolves.3. particles.5 1. or Z0 .

25 0. .05 0 0 5 Z’ 10 ΔT=0 Δ T = 0.5 0 1 2 3 Z 4 5 Figure 6. All particles are located at Z = 2 at T = 0.1 0.0001 Δ T = 0. The distributions are taken after various inter-acquisition times. ∆T .15 0.59 1.01 Δ T = 0.2 PDF 0.5: Spatial distribution of small particles at various times due to hindered diﬀusion.5 1 PDF ΔT=0 Δ T = 0.5 ΔT=1 ΔT=5 0.6: Spatial distribution of particles located within the range of 1 < Z < 5 at T = 0.001 Δ T = 0.1 ΔT=1 Δ T = 10 15 Figure 6. 0.1 Δ T = 0.3 Δ T = 0.

V = ∆X /∆T .7: Percentage of particles in the imaging range for diﬀerent inter-acquisition time. however. the focus is on the eﬀect of shear on apparent velocity measurements. which is in agreement with a separate numerical study conducted by Sadr et al.8 is the distribution of non-dimensional apparent velocity. or equivalently the shear rates. [80] and Huang et al. or ∆t = 0.0 < Z0 < 3. this percentage drops to 65% if the inter-acquisition time is 10 msec. The imaging range is the same as the initial particle distribution range.2.0 1. present less of a problem for Particle Tracking Velocimetry (PTV) as the technique makes an eﬀort to distinguish the particle drop-in’s and drop-out’s. which are particles that do not drop out. the acquisitions should be taken with ∆T < 0. Shown in ﬁgure 6. the major concern for PIV is the percentage of particle drop-in’s and drop-out’s because all imageable particles at the time of image acquisition are analyzed without any eﬀort to distinguish the entering and the leaving. emulating physical TIRV measurements. In dimensional terms. The percentage of particles that do not drop out for various inter-acquisition time is shown in 6. more than 90% of 100-nm particles remain in the imaging range of 100 < z < 300 nm (10% drop-out) if image acquisitions are taken at 1 msec apart.5 msec for 100-nm radius tracer particles. a longer times between consecutive acquisition results in a lower percentage of “good” particles. near-wall PIV measurement with sub-micron particles should be conducted with a inter-acquisition time as short as possible to ensure accuracy. Based on this result.60 100 % Remaining in Imaging Range 90 80 70 60 50 40 30 0 2 4 6 8 10 1. [85]. suggested that the increasing skewness and widening of the apparent velocity distribution . in measurements. P e.3.0 < Z0 < 5. In particular. Z0 .7. The dropout’s. If an acceptable percentage of drop-out’s is 95%.0 < Z0 < 5.0 3.4 Horizontal Apparent Velocity Distributions Subsequent analysis concentrates on horizontal motion of particles that do not drop out. As mentioned previously. [59] Not surprisingly. for particles under various Peclet number. 6. This agrees well with experimentally measured PDF’s reported by Jin et al. It is clearly observable that the apparent velocity PDF’s widen and skew as shear rate increases. Jin et al. However.0 ΔT Figure 6.

Vavg is the mean of each apparent velocity PDF.6 PDF Pe = 0.8 0. larger P e has a narrower but more skewed normalized PDF.61 0. In general.5 Pe = 1 Pe = 3 Pe = 5 Pe = 10 Pe = 30 0.9: Normalized apparent velocity distribution of particles remaining in the imaging range 1 < Z < 3 after ∆T = 10.8: Apparent velocity distribution of particles remaining in the imaging range 1 < Z < 3 after ∆T = 10. 1. width.5 Pe = 1 Pe = 3 Pe = 5 Pe = 10 0.5 1 PDF Pe = 0. . and skewness.2 0 0 10 20 V 30 40 50 Figure 6.3 Pe = 0.5 0 −3 −2 −1 (V−V 0 avg 1 )/V avg 2 3 Figure 6. The normalized PDF’s collapse onto each other at P e > 3. Larger P e leads to an apparent velocity distribution with larger mean.4 0.

[85].02 0. It is noted that the collapsed PDF’s for P e > 3 have a smaller distribution width but a larger skewness. and the agreement of BD simulations further validates the presented conclusion.10 that the apparent velocity PDF’s of imaging ranges farther away from the wall are wider and less skewed than that of imaging ranges closer to the wall.12. it is observed that diﬀusion is quite dominant at small ∆T . the horizontal displacement of the particle ensemble is dominated by diﬀusion. One can observe in ﬁgure 6. the time evolution of apparent velocity distributions was examined and shown in ﬁgure 6. leading to apparent . while the distributions of P e < 3 are wider but more symmetric.9. as shown in ﬁgure 6. The explanation is that at low shear rates.5 Time Evolution of Apparent Velocity Distributions Finally.03 PDF 0. the ﬁnite thickness of the imaging range and shear eﬀect give rise to the skewness and distribution widening.05 1 < Z0 < 2 0. as plotted in ﬁgure 6.01 0 0 2 < Z0 < 3 3 < Z0 < 4 4 < Z0 < 5 5 < Z0 < 6 50 V 100 150 Figure 6. All apparent velocity distributions are measured at ∆T = 10 and P e = 10. This physical explanation is supported by the fact that both skewness and distribution width are scalable by the shear rate only at P e > 3. Another source of apparent velocity distribution skewness is the hindered diﬀusion and the presence of the wall. At high shear rates.10: Apparent velocity distribution of particles at various imaging ranges.3. violates the symmetric PDF assumption of PIV analysis and could lead to measurement errors. on the other hand. it is observed that the apparent velocity PDF’s can collapse onto a single distribution for P e > 3. The combined eﬀect of the hindered diﬀusion and the shear-induced rotational slow-down in the near-wall region causes the apparent velocity PDF’s to skew. Upon further analysis. and their distributions are more symmetric due to less inﬂuence of the wall and hindered diﬀusion. while at far away the wall presence is not felt and the symmetric distributions again show scaling similarity. The same shear-dominance eﬀect at P e > 3 has been reported experimentally by Huang et al. For a ﬁxed P e. 6. Particles that start oﬀ farther away from the surface move faster because they are carried by ﬂuids at higher velocity planes.11. The diﬀerence is even more obvious if each PDF is re-scaled by its distribution mean.04 0. Vavg . leading to a wider normalized PDF.62 0.

01 Δ T = 0.12: Time evolution of apparent velocity distribution. Note that the apparent velocity distribution narrows and skews with increasing inter-acquisition time.03 PDF 0.01 0.05 1 < Z0 < 2 0.0001 Δ T = 0. All apparent velocity PDF’s are obtained at P e = 30 and with particles within the imaging range of 1 < Z < 3 at T = 0. .01 0 −100 2 < Z0 < 3 3 < Z0 < 4 4 < Z0 < 5 5 < Z0 < 6 6 < Z0 < 7 7 < Z0 < 8 −50 0 V − Vavg 50 100 Figure 6.01 Δ T = 0.11: Collapsed apparent velocity distribution shown in ﬁgure 6.1 ΔT=1 Δ T = 10 0 V 100 200 300 400 Figure 6. 0.025 0.015 PDF 0. Vavg .04 0.02 0.005 0 −300 −200 −100 Δ T = 0. ∆T .02 0.63 0. The PDF’s are scaled by subtracting their corresponding distribution mean.10.

3 Pe = 0.95 0.1 1.64 1.15 Vavg/Vshear 1.12. . Vshear is the calculated velocity of the particles in a near-wall shear ﬂow if there is no Brownian motion. and is the target quantity that velocimetry is trying to measure. All mean apparent velocities are obtained from particles that remained at imaging range of 1 < Z < 3.05 1 0.5 Pe = 1 Pe = 3 Pe = 5 Pe = 10 Pe = 30 8 10 Figure 6.13: Time evolution of mean particle apparent velocity.9 0 2 4 ΔT 6 Pe = 0. Thus Vavg /Vshear can be interpreted as the accuracy of velocimetry measurement. Each data point represents the mean value of one apparent velocity distribution shown in ﬁgure 6. Note that data of all P e show a minimum velocity ratio at approximately ∆T = 1.

The velocity ratio would keep increasing as ∆T increases. With further analysis. If Vshear is deﬁned as the mean velocity of all ﬂuidic planes inside the imaging range and Vavg is the mean value of an apparent velocity distribution such as the ones shown in ﬁgure 6. except near the minimum. For each data series. Figures 6. [59] suggested an alternative time scale. the imaging range is set at 1 < Z < W and the non-dimensional time is rescaled with 1/W 2 .2 1.9 −3 10 10 −2 10 −1 10 0 10 1 ΔT/W2 Figure 6.12 as ∆T increases. The time dependence of the velocity ratio Vavg /Vshear is shown in ﬁgure 6. Vavg /Vshear . This alternative time scale. Thus diﬀusion accounts for a large fraction of the measured apparent velocity at short inter-acquisition time. This explains the narrowing of the apparent velocity distributions in ﬁgure 6. collapse onto each other under this rescaled time scheme. Note that the velocity ratios. Due to increased shear dominance. it can be observed that the values of ∆T at which the minima of Vavg /Vshear ratio occur depend on the thickness of the imaging range. All data series have P e = 30.65 1.3 Vavg/Vshear 1. then Vavg /Vshear can be interpreted as velocimetry measurement accuracy with Vavg /Vshear = 1 being the ideal measurement. it would be of interest to see if the mean value of the velocity distributions evolve as a function of time as well.5 W=2 W=4 W=6 W=8 W = 10 1.12 and 6.13 demonstrate that both the shape and the mean of an apparent velocity distribution are not time-invariant.12) while the shear-induced ﬂow velocity distribution width scales linearly with ∆T . while the majority of the measure velocity is due to the shear ﬂow at large ∆T .14: Rescaled time evolution of mean particle apparent velocity. ∆X ∼ √ ∆T ⇒ V = 1 ∆X ∼√ . It can be observed that all Vavg /Vshear ratios exhibit the form of a concave-up function of ∆T . can be interpreted as the time it takes for a particle in contact . Minimal velocity ratios for all W ’s occur near an alternative non-dimensional time scale of ∆T /W 2 ≈ 10−1 . ∆T ∆T (6. with a minimum occurring at approximately ∆T = 1. Clearly. the apparent velocity distribution narrows as time increases. if the imaging range is deﬁned at 1 < Z < W . therefore.1 1 0.12.4 1. In their paper Sadr et al. velocity distributions that are signiﬁcantly wider than that of at large ∆T . The goal of vecimetry measurements is to accurately estimate ﬂuid velocities using the tracer particle apparent velocity as an estimator. ∆T /W 2 . Such change can be explained by the fact diﬀusive velocity distribution wideth scales with ∆T −1/2 .13. if the apparent velocity distributions evolve with time.

For small ∆T .14. used the Fokker-Planck approach to study the PDF of ﬂuidic planes that an ensemble of particles would have sampled between image acquisitions in nano-PIV. The time dependence of this ratio is in striking resemblance to that shown in ﬁgure 6. the turning point in the relative contribution of the two groups of particles (the ones that move closer to the surface and the ones that sample the higher shear plane and return) occurs at ∆T /W 2 ≈ 10−1 .13 and 6.13 that the velocity ratio is P e- . with the wall to diﬀuse out of imaging range due to Brownian motion. Two potential paths of a particle are shown in this ﬁgure. That is. it samples the higher velocities of planes that are out of the imaging range. The larger the ∆T . the physical reasoning described in the previous paragraph suggests that the thickness of the imaging range would be an important parameter.15.15. and thus the mean apparent velocity decreases. Clearly. it should be noted that in both ﬁgures 6. the higher probability that particles can sample farther away from the surface and still manage to return to the imaging range at the time of second image acquisition. and increases monotonically afterward? The answer to this question lies in ﬁgure 6.14 demonstrates that the velocity ratio Vavg /Vshear also has a scaling similarity. such path 2 illustrated in ﬁgure 6.5 and is illustrated in ﬁgure 6. Figures 6. Vavg /Vshear → 0 at ∆T → 0 as the instantaneous apparent velocities of particles would be the closest to the local ﬂuidic velocities. Using this non-dimensional time scale. the consequence is that the tracer particles sample toward the lower velocity planes. This suggests that the percentage of particle drop-out and the positions whose ﬂuidic velocities are sampled by the particles play a crucial role in the accuracy of velocimetry measurements. one can observe in ﬁgure 6.15 is more likely to be taken than path 2. On the other hand for large ∆T . these contributions of ﬂuidic velocities outside of the imaging range are reﬂected in the higher values of mean particle apparent velocities. In both cases. Between image acquisitions. In addition.66 path 2 path 1 Imaging range Figure 6. it samples the velocities of the lower planes and thus translates a short horizontal distance. If the particle takes path 1. particles that have taken diﬀerent paths could have travelled diﬀerent distances while sampling diﬀerent velocities along the way. Because they have sampled the ﬂuidic velocities of the higher shear planes. On the other hand if the particle takes path 2.14 can also serve as guides for choosing the appropriate ∆T for near-wall particle tracking velocimetry. and thus translates a larger horizontal distance. which justiﬁes the scaling of non-dimensional time ∆T with 1/W 2 . First. path 1 in ﬁgure 6. Indeed Sadr et al. They obtained a ratio of averaged Z value sampled by the particles to the mid-distance of the imaging range. So why is the velocity ratio minimal at ∆T /W 2 ≈ 10−1 . (W + 1) /2.15: Schematic of 2 potential paths for particle translation.14. some of the particles that have left the imaging range are given enough time to return at the second acquisition. ﬁgure 6. Since drop-out’s are less signiﬁcant for small ∆T .9 and 6. the skewed distribution of particles toward the wall suggests that the imaged particles are more likely to move closer to the wall.

4 CONCLUDING REMARKS Brownian dynamics simulation oﬀers an attractive approach to the study of near-wall particle dynamics. velocity distributions evolve as a function of time. with hindered diﬀusion also contributing to changes in the velocity distribution width and its skewness. PIV will remain accurate as long as the time between acquisition is much smaller than the diﬀusion time of tracer particles. Furthermore. with results conﬁrmed by experimental data. and the problem can be mathematically closed by specifying a Peclet number and a sedimentation constant. The potential error of both methods would stem from biased sampling of the velocities at various shear planes. By using it as a scaling guide. colloidal particle motion is dominated by shear when Peclet number is greater than 3. These observations suggest that choosing an inter-acquisition time of ∆T /W 2 ∼ O 10−1 would most likely yield measurement inaccuracy. In near-wall colloidal dynamics. In the direction parallel to the wall. PTV and SPTV (Statistical Particle Tracking Velocimetry) [94] are much more reliable measurements because PTV attempts to exclude particle drop-in’s and drop-out’s while SPTV treats the drop-in’s and drop-out’s as statistical noise. It can be clearly observed that the “dip” in velocity ratio depends on the values of W . the incapability of imaging equipments to make consecutive image acquisitions with an extremely short inter-acquisition time would limit the applicability of PIV in near-wall measurements. reporting mean velocities that are time-dependent with a minimum at ∆T /W 2 ≈ 10−1 . An alternative method is to calculate which inter-acquisition time would result in the measured mean velocity being equal to the shear-induced velocity before experiments are conducted. Neither correction method can be applied to PIV measurements. Thus the selection of ∆T such that the velocity ratio would be minimum should be avoided.14 is not W -invariant in regions near the minimum. physical length and time scales are particle radius and diﬀusive time. where large W values lead to a lower minimal velocity ratios. the correct shear-induced velocity of the particles can be retrieved from the measured mean velocity values. while the velocity ratio shows no dependence on W at both the higher and lower ends of the time scale ∆T /W 2 . As tracer particles get smaller and their diﬀusion become greater. . hindered diﬀusion skews the displacement distributions toward to wall. We demonstrate that wall-induced hindered diﬀusion and translational slow-down of a colloidal particle in a simple shear ﬂow can be accurately captured by Brownian dynamics simulations. This study also provides an assessment tool to the relative accuracy of near-wall PIV and PTV. In the direction perpendicular to the wall.14 oﬀers a way to correct for this bias. 6. On the other hand. Because of a large amount of drop-in’s and drop-outs when nanoparticles are used. the inaccuracy of PIV in near-wall measurement could be signiﬁcant. Such avoidance is further reinforced by the observation that the velocity ratio in ﬁgure 6. ﬁgure 6. However.67 invariant except near the minimum where ﬂuctuations exist.

quantum dots have been viewed as the next generation of tracer probes. TIRV can also be applied to experimentally investigate ﬂow characteristics within the gas boundary layer. These quantum dots are small (a few nanometer in diameter). Thus a new breed of tracer particles or molecules in the order of 1 nanometer would be needed. advancement of technology would soon deem particles of 100 nanometer insuﬃcient in probing the near-wall region as scientists would like to look even closer to the solid surface.Chapter 7 Concluding Remarks and Suggested Studies In this dissertation we have presented our experimental studies of aqueous solution boundary slip and anisotropic hindered diﬀusion. and their usage under evanescent wave imaging settings have been demonstrated by Pouya et al. In fact. and if the solid surface charges would interact with the weak charges carried by the solve molecules. Besides binding. It would certainly be of scientiﬁc interest to see if the solvent molecular polarity would have an eﬀect on boundary slip. and described the total internal reﬂection velocimetry (TIRV) method used in these experiments. thus making them an ideal candidate to probe regions that are even closer to the wall with a variety 68 . Of course. The area of interest include both speciﬁc and non-speciﬁc binding of suspensions and the solid boundary. Understandably. more uniform in size than polystyrene ﬂuorescent particles. In addition. [100] and Guasto et al. First of all in pursuing a better understanding of boundary slip. [94]. and their chemical properties are vastly diﬀerent from the non-polar group of solvents. such as ligands and receptors to study blood cell adhesion. Water and similar solvents such as alcohols have a polar molecular conﬁguration. and the TIRV technique is ideal for studying these phenomena. Returning to the liquid phase. such as hexane and toluene. Furthermore. The TIRV technique can certainly be extended to near-surface measurements in a gas phase. Although the existence of boundary slip at a gas/solid interface has been well documented. kinetics of surface-based chemical reactions can also be studied with the same mechanism. these studies open up opportunities for future experimental works in the areas of ﬂuid mechanics and colloidal science. A Brownian dynamics simulation study is also presented to compare the eﬀectiveness and accuracy of TIRV and nano-PIV. particle or cell adhesion and desorption are both areas of great interests in colloidal science and biology. ﬂuorescent aerosols would be required as tracer particles. To investigate speciﬁc chemical binding. water is by no means the only test ﬂuid of interest. the TIRV technique oﬀers a method to make direct measurement of the gas slip velocities. the particles and the solid boundary surface can be coated with molecules that bind correspondingly. and available in water or organic solvent soluble forms. and we believe such technology is possible in the near future.

provided that experimental parameters such as camera noise. The Brownian motion of these quantum dots is undoubtedly much more signiﬁcant and the particle tracking method in the TIRV will be incapable of dealing with the large proportion of particle drop-in’s and drop-out’s between image acquisitions. however. The SPTV thus eliminates the needs to keep track of particle drop-in’s and drop-out’s and to unambiguously matching detected particles. especially in near-surface measurements. . a high seeding density might be desirable to preserve the particle-particle interactions and/or to increase measurement eﬃciency. An additional limitation of the particletracking based TIRV is its requirement of low particle seeding density to avoid tracking ambiguity. Perhaps a more accurate measurement of the slip velocities can be achieved by using quantum dots in TIRV. They proposed that the true statistics of the desired physical displacement can be extracted by matching each detected particle to all others. and seeding density are known. In some experimental situations.69 of liquids. [94] is a perfect solution to these problems. It is certainly more advantageous than other particle-based velocimetries. The statistical particle tracking velocimetry (SPTV) developed by Guasto et al. particle size and diﬀusivity. imaging depth.

such measurement is extremely diﬃcult. The best ﬁt line was then extended to φ greater than critical angle to determine incident angle. respectively.2). and this relation should be true for all incident angles despite of total internal reﬂection.1) where n1 and n2 are refractive indices of glass and air. The refracted beam in air is then projected to a far-away wall or ceiling where the refractive angle can be measured accurately (shown in ﬁgure A. x. as shown in ﬁgure 2. The illumination laser beam is directed into the objective lens by passing through the a converging lens. The empirical equation was found to accurately predict the lens position of critical angle. it would be ideal if one can measure the beam incident angle directly when determining the penetration depth. the total internal reﬂection was created at the glass/water interface by directing a laser beam through a microscope objective lens. and sin θ. Knowing the beam incident angle is critical in determining evanescent ﬁeld penetration depth. The beam is then allowed to refract at a glass/air interface. To determine this relation. In practice. an empirical linear relation between x and sin φ was found (shown in ﬁgure A. Using equation (A.1). Thus a geometric relation should exist between the the lens translation distance and the beam incident angle. because the total internal reﬂection bends the reﬂected beam back into the objective lens. (A.3).Appendix A Calibration of beam incident angle In our TIRV setup.1. In this appendix. the laser beam is directed through the objective as used in a non-TIRF setup. The bending of the beam is achieved by translating the converging lens [47]. the measurement method of the illumination beam incident angle is presented.3). as shown in ﬁgure A. Snell’s law determines the refraction angle by n1 sin φ = n2 sin θ. By examining the data. As demonstrated in equation (2. 70 . we found a linear relationship between the lens position.1.

71 θ Air φ Glass Figure A.1: Schematic of laser beam refraction at the glass/air interface.1. . θ Figure A.2: Photo and schematic of beam incident angle measurement. The refraction angle θ is the same as that of ﬁgure A.

8 Data Linear fit 0. .5 10 x (mm) 10.4 0.2 8.72 0.5 sin(φ) 9 9.5 11 Figure A.6 0.33 x + 3. converging lens position.5 0 −0.2 sin(φ) = − 0.3: Plot of laser beam angle vs.

Appendix B

**Shear-induced lift force (or more precisely, lack of ) on near-wall submicron-particles
**

It has been suggested that a shear-induced lift force can act on suspended particles in a linear shear ﬂow, making them more likely to move away from a solid boundary. This would result in a non-uniform distribution of particles near our glass solid surface, where our total internal reﬂection velocimetry (TIRV) measurements take place. Because our statistical analysis is based on the assumption of uniform particle distribution, the shear-induced lift force would lead to signiﬁcant inaccuracies. However, we believe that such a lift force is insigniﬁcant in our ﬂow regime, and in this appendix, an established theory is presented to support our argument. The subject of lift forces acting on a small sphere in a wall-bounded linear shear ﬂow has been thoroughly studied by Cherukat & McLaughlin [87]. Here we will present only the theory that applies to the ﬂow conditions under consideration. Suppose that a free-rotating rigid sphere of radius a is in a Newtonian incompressible ﬂuid of kinematic viscosity ν and is in the vicinity of a solid wall. In the presence of a linear shear ﬂow, the free-rotating sphere can can travel at a velocity Usph that is diﬀerent from the ﬂuid velocity, UG , of the shear plane located at its center [38]. We can deﬁne a characteristic Reynolds number based on the velocity diﬀerence, Us = Usph − UG , with Res = Us a . ν (B.1)

Another characteristic Reynolds number based on shear rate can be deﬁned as ReG = Ga2 , ν (B.2)

where G is the wall shear rate. In this geometry, the wall can be considered as located in the ”inner region” of ﬂow around the particle if Res κ and ReG κ2 , where κ ≡ a/h and h is the distance between the particle’s center and the wall. For near-wall particle velocimetry described in chapters 3 and 4, Res ∼ ReG ∼ 10−7 while κ ∼ O (1), and thus the inner region theory of lift force applies. For a ﬂat wall located in the inner region of ﬂow around a free-rotating particle, the lift force, FL , which is perpendicular to the wall, is scaled by [87] FL ∼ Res · I, (B.3)

73

74 where I is a coeﬃcient that can be numerically estimated by I = 1.7631 + 0.3561κ − 1.1837κ2 + 0.845163κ3 − 3.21439 + 2.6760 + 0.8248κ − 0.4616κ2 κ ReG Res +

2

(B.4) .

1.8081 + 0.879585κ − 1.9009κ2 + 0.98149κ3

ReG Res

Again for the velocimetry conditions described in chapters 3 and 4, I ∼ O 102 . Therefore FL ∼ Res · I 10−7 102 1, (B.5)

and the lift force acting on near-wall particles is insigniﬁcant and can be neglected for all practical purposes.

Appendix C

**Evanescent wave image of micron-sized ﬂuorescent particles
**

Imaging of ﬂuorescent nanoparticles under TIRFM have been well reported by many groups, particularly in the exponential decay relation between particle intensity and its distance to the substrate surface [44, 85, 90]. But for micron-sized ﬂuorescent particles in evanescent ﬁeld, there has been no report on their imaging characteristics. In this appendix, numerical simulations were performed to investigate some of the imaging characteristics associated with ﬂuorescent particles under evanescent wave imaging. The numerical simulation was conducted in the commercially packaged COMSOL Multiphysics software environment. The simulation geometry is simpliﬁed from three-dimensional to twodimensional but is still a representative of near-surface imaging, and shown in ﬁgure C.1. Polystyrene particles (refractive index 1.59) of three diﬀerent diameters, d/λ = 0.39, 6 and 12 where λ is the incident beam wavelength, are immersed in the water phase (refractive index 1.33) and placed in the vicinity of the glass phase (refractive index 1.51). A Gaussian beam enters from the lower-left boundary and reﬂects oﬀ the water/glass interface at a 64.54◦ angle, while scattering boundary conditions are applied to all other external boundaries. Simulations were repeated for various gap sizes, h, between the particle and the glass, with h/λ ranging from 0 to 2. The eﬀectiveness of the COMSOL Multiphysics package in modelling total internal reﬂection and evanescent ﬁeld was ﬁrst demonstrated in the absence of a polystyrene particle, and is shown in ﬁgure C.2. The simulation model perfectly captures total internal reﬂection and an exponential decay of evanescent energy density in the water phase is found to be in agreement with theories (shown in ﬁgure C.3). Time-averaged energy densities of particles in evanescent ﬁeld are shown in ﬁgures C.4, C.5 and C.6, respectively. In ﬁgure C.4, it can be observed that the presence of a particle with diameter d/λ = 0.39 does not distort the energy ﬁeld. In contrast, larger particles such as d/λ = 6 and 12 can distort the energy ﬁeld quite signiﬁcantly. Their presence can be seen to create a shadow in the reﬂected beam. These lost energy leaks into the interior of the large particles through a “frustrated-total internal reﬂection mechanism”, illuminating regions beyond the penetration depth of evanescent wave. These energy continue to reﬂect and refract at the polystyrene/water interface, resulting in a high energy density in the lower-right side of the particle, while some additional energy escapes into the right half of the water phase. Using the subdomain integration function of COMSOL, one can ﬁnd out the overall energies inside the polystyrene particles. This quantity is important because in TIRFM experiments, only the light emitted by the ﬂuorophores inside the polystyrene particles is imageable, and the ﬂuorophores are excited only by the light energy that enters the particles. The overall energies that 75

except the presence of a suspended particle. a total internal reﬂection occurs at the glass/water interface. Scattering (or ﬂoating) boundary condition is applied to all external boundaries at the water and glass phases.2: COMSOL simulation of total internal reﬂection. The geometry of this simulation is identical to that of ﬁgure C.1: Schematic of COMSOL simulation geometry. Figure C. .76 Polystyrene Particle Water Phase Glass Phase Incident Gaussian Beam Figure C. Because the incident angle of the Gaussian beam is 64. Plotted in the ﬁgure is time-averaged total energy density of total internal reﬂection at a glass/water interface. A polystyrene particle is suspended in the water phase and located in the vicinity of glass’interface. The particle shown in the ﬁgure has a diameter of d/λ = 6. except at the boundary inside the glass phase where the incident Gaussian beam enters.54◦ .1.

except that the particle diameter is with d/λ = 0.77 1 Simulation Theory Normalized Intensity 0.39 in evanescent ﬁeld.4: COMSOL simulation of a particle with d/λ = 0. Plotted in the ﬁgure is time-averaged total energy density.4 0.39 and the gap size between the particle and the glass surface is h/λ = 0. and the geometry of this simulation is identical to that of ﬁgure C. Close agreement between simulation results and theoretical calculations is obtained.2 0 0 0.8 0.1.5 2 Figure C. .6 0. Particle Figure C.5 1 h/λ 1.3: The exponential intensity decay of evanescent ﬁeld in ﬁgure C.1.2.

1. Plotted in the ﬁgure is time-averaged total energy density. except that the gap size between the particle and the glass surface is h/λ = 0. except that the particle diameter is d/λ = 12 and the gap size between the particle and the glass surface is h/λ = 0.5: COMSOL simulation of a particle with d/λ = 6 in evanescent ﬁeld. Figure C. .1.1. Plotted in the ﬁgure is time-averaged total energy density. and the geometry of this simulation is identical to that of ﬁgure C. and the geometry of this simulation is identical to that of ﬁgure C.6: COMSOL simulation of a particle with d/λ = 12 in evanescent ﬁeld.78 Figure C.1.

39) follows an exponential decay function that is identical to the evanescent energy decay. This forms the basis of using the overall intensity of nanoparticles for 3D displacement tracking. does not follow the same exponential decay function of the evanescent ﬁeld. However. The intensities are normalized by the intensity observed when the particle is in contact with the glass surface. however. the overall intensity of a small particle (d/λ = 0. such a convolution is computationally complicated and expensive.5 2 Figure C. a is the radius of the objective lens and f is the objective focal length. high magnitude objective whose focal depth.7: Overall evanescent energy in the suspended particles at various gap sizes.2) Here λ is the wavelength. δ.7. The evanescent ﬁeld intensity is obtained from the cross-sectional time-averaged total energy density proﬁle of ﬁgure C. (C. enter the particles at gap sizes h/λ ranging from 0 to 2 is shown in ﬁgure C. As it has been demonstrated by Huang et al. For a point light source that is a distance z oﬀ the focal plane. [85] and Sarkar et al. The overall intensity of larger particles. it’s intensity is [101] sin (u/4) 2 I (z) = I0 (C.79 1 0.7.2 0 0 d/λ = 0. This is probably due to the fact that a larger radius of curvature provides more surface area for light to leak into the particles through the frustrated-total internal reﬂection mechanism. A simpler way is to look at the intensity proﬁle when the ﬂuorescent energy is projected onto the focal plane.6 0. A more relative question is what will a ﬂuorescent particle with diameter greater than the illumination wavelength look like under a high numerical aperture (NA).1) u/4 where I0 is the point source emission intensity and u= 2π λ a f 2 z. [90]. One of the ways to ﬁnd out is to convolute the energy density inside the particles with diﬀraction equation and point spread function.39 d/λ = 6 d/λ = 12 Evanescent Field Normalized Intensity 0. In . with which one could still gain some qualitative understanding of the image. particularly at small gap sizes.4 0. a near-exponential dependency of large particle intensity on the gap size is observed in ﬁgure C.8 0. Still.5 1 h/λ 1.2. is roughly δ/λ = 2.

The intensity projection of a particle with d/λ = 6 is shown in ﬁgure C. The direction of the evanescent wave propagation is toward positive x/λ. z) · zdz (C. a/f is commonly referred to as the f-number of lens and for a microscope objective. which is important in microscopy.8 as blue squares. I0 is the peak intensity and x/λ = 0 corresponds to the particle geometric center. the intensity proﬁle from actual imaging of a particle appears to be wider than that of the simulated result. z) is calculated using equation (C.4 0. This leads to physical inaccuracy as we will demonstrate subsequently. This projection is obviously 0 a simpliﬁed calculation as it assumes negligible diﬀraction. the . The red dotted line. represents the projected intensity proﬁle based on results of COMSOL simulation of a particle of the same size and equation (C.9. it is assumed that both a and f are much larger than λ. A peak intensity near the center can be clearly observed in the image. This is due to the fact that the computation leading to the projection (red dotted line) in ﬁgure C.8 0.3). For comparison. However. A TIRFM image of a 3-µm particle (equivalently d/λ = 6) is shown in ﬁgure C. its projected intensity at point x = x0 on the z = z0 plane is [101] 2a−b Ip (xo ) = b I (x0 .80 1 0.8 as a red dotted line. Therefore. however. for a particle in contact of the wall and its center is located at x = 0 and z = a.2 0 −4 −2 0 2 4 x/λ Figure C.1). In the projection.9 is also shown in ﬁgure C. while a longer tail is observed in the direction of the laser beam propagation. This intensity proﬁle is similar in shape when compared to that of red dotted line from simulation. the intensity exhibits a peak value near the particle center. getting equation (C.3) where b = a− a2 − x2 and I (x0 .9.6 I/I0 0. it is equal to the numerical aperture [73]. A peak intensity is found near the particle center. while a slightly longer tail is found in the direction of evanescent wave propagation. Nevertheless. where the focal plane is set at the glass surface.8 neglects diﬀraction of light.8: Cross-sectional intensity proﬁle of a 3-µm particle (d/λ = 6). The blue squares represent the cross-section intensity proﬁle indicated as a red line in ﬁgure C. a cross-sectional intensity proﬁle of ﬁgure C.1).

3) is narrower than that of an actual image because of the neglected diﬀraction in numerical integration.9: Digital image of a 3-µm particle (d/λ = 6) in contact with glass surface. toward the right tip. .10. we can again see that there is a bright peak near its center. In addition. blue squares). while the asymmetric tail on the right side is even more pronounced. However.81 1 µm Figure C.1) and (C. Again. The intensity proﬁle along the red cross-section shown is plotted in ﬁgure C. With a particle of this size. which can be also be observed in the right tail of the red simulation intensity proﬁle in ﬁgure C. the intensity proﬁle obtained from the simulation results and equation (C. The same imaging projection is also performed for a 6-µm particle (d/λ = 12) and shown in ﬁgure C. as observed in ﬁgure C.8.3). there are small.10.11) as well as on a cross-sectional intensity proﬁle (ﬁgure C. the modelling results and the actual image show qualitative agreement despite the simplicity of the integration model in equations (C. resemblance of of the two proﬁles is striking and the proﬁles are in qualitative agreement. alternating regions of bright spots. A similar observation can be made on an actual image of a 6-µm particle (ﬁgure C.8.10. A large bright center is clearly visible while the right half of the particle is signiﬁcantly brighter.

8 I/I 0 0. The direction of the evanescent wave propagation is toward positive x/λ.11. The blue squares represent the cross-section intensity proﬁle indicated as a red line in ﬁgure C.11: Digital image of a 6-µm particle (d/λ = 12) in contact with glass surface.3). I0 is the peak intensity and x/λ = 0 corresponds to the particle geometric center. however. 2 µm Figure C. The intensity proﬁle along the red cross-section shown is plotted in ﬁgure C.2 0 −6 −4 −2 0 2 4 6 x/λ Figure C. The red line.10: Cross-sectional intensity proﬁle of a 6-µm particle (d/λ = 12). .10.6 0.4 0.82 1 0. represents the projected intensity proﬁle based on results of COMSOL simulation of a particle of the same size and equation (C.

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