INKJET PRINTING FOR SURFACE ENERGY CONTROL TOWARDS TAILORED

WETTING CHARACTERISTICS

By

KENT ANDREW EVANS

A thesis submitted in partial fulfillment of

the requirements for the degree of

MASTER OF SCIENCE IN MECHANICAL ENGINEERING

WASHINGTON STATE UNIVERSITY

School of Mechanical and Materials Engineering

DECEMBER 2017

© Copyright by KENT ANDREW EVANS, 2017

All Rights Reserved
© Copyright by KENT ANDREW EVANS, 2017
All Rights Reserved
To the Faculty of Washington State University:

The members of the Committee appointed to examine the thesis of KENT ANDREW

EVANS find it satisfactory and recommend that it be accepted.

Arda Gozen, Ph.D., Chair

Weihong Zhong, Ph.D.

Lei Li, Ph.D.

ii
 ACKNOWLEDGMENT

This thesis would not have been possible without the help of a few individuals. I extend my

sincere thanks to all of them. I would like to thank my mother and father for their tireless

support. I would also like to thank Casey for putting up with my foul moods during hard times

and always providing me with the strength and support to persevere, regardless of the situation.

Thank you to Abhishek Gannarapu, Sepehr Nesaei, and Dr. Arda Gozen for their seemingly

endless supply of ideas and insight. Special thanks to Dr. Lei Li and Dr. Rongrong Sun for their

assistance with the focal length measurements and use of their equipment.

iii
 INKJET PRINTING FOR SURFACE ENERGY CONTROL TOWARDS TAILORED

WETTING CHARACTERISTICS

Abstract

by Kent Andrew Evans, M.S.

Washington State University
December 2017

Chair: Arda Gozen

Control of surface properties is of paramount importance in numerous applications

including biomedical, naval, microfluidic, and micro-optics. The intrinsic advantages of additive

manufacturing, specifically inkjet printing, allow for unprecedented control over the spatial

resolution and ad-hoc patterning of thin films on target substrates. Leveraging these advantages,

this thesis outlines a method through which the wettability of a surface is controlled through

printing of thin, hydrophobic films using inkjet printing. The contact angle of a commercial

micro-optics material is characterized both at small scale (10’s of micrometers) with single films

and large scale (multiple millimeters) with large patterns of films. A model is shown that

correlates large scale contact angles to specific printing parameters such as film pitch and ink

concentration. This work will inform future studies on surface property control through inkjet

printing for various applications.

iv
 TABLE OF CONTENTS

Page

ACKNOWLEDGMENTS ............................................................................................................. iii

ABSTRACT ................................................................................................................................... iv

LIST OF TABLES ......................................................................................................................... vi

LIST OF FIGURES ...................................................................................................................... vii

SECTION

SECTION ONE: INTRODUCTION ...................................................................................1

SECTION TWO: BACKGROUND ....................................................................................5

SECTION THREE: METHODOLOGY AND RESULTS..................................................8

SECTION FOUR: CONCLUSION ...................................................................................31

REFERENCES ..............................................................................................................................32

v
 LIST OF TABLES

Page

Table 1.1.1: Optimal Waveform Parameters .................................................................................14

vi
 LIST OF FIGURES

Page

Figure 1.1.1: Young’s Law Schematic ............................................................................................2

Figure 3.1.1: General Process Schematic ........................................................................................8

Figure 3.2.1: Inkjet Printing System ................................................................................................9

Figure 3.2.2: Example LabVIEW VI .............................................................................................10

Figure 3.2.3: Basic Inkjet Dispensing ............................................................................................11

Figure 3.2.4: Typical Inkjet Waveform .........................................................................................12

Figure 3.3.1: Delta Assist VI .........................................................................................................16

Figure 3.3.2: Small Scale Droplets ................................................................................................17

Figure 3.3.3: Contact Angle vs. PDMS Concentration ..................................................................18

Figure 3.3.4: AFM Force Curves ...................................................................................................20

Figure 3.3.5: Coated AFM Tip Retraction Schematic ...................................................................21

Figure 3.3.6: PDMS Film Characteristics ......................................................................................22

Figure 3.3.7: The Halo Effect ........................................................................................................23

Figure 3.3.8: Pendant Drop Image .................................................................................................25

Figure 3.4.1: Cassie-Baxter Equation Schematic ..........................................................................26

Figure 3.4.2: Model Unit Cells ......................................................................................................27

Figure 3.4.3: Predicted and Expected Large Scale Droplet Contact Angles .................................27

Figure 3.4.4: Large Scale Droplet Images .....................................................................................28

Figure 3.5.1: Printed Micro-Fluidic Device ...................................................................................29

Figure 3.5.2: Fabricated Micro-Lens Array ...................................................................................30

vii
 Dedication

For Casey, Max, Dany, and my family and friends

I could not have done it without you

viii
 SECTION ONE: INTRODUCTION

Micro-engineered surfaces with controlled properties are quickly gaining importance in

our everyday lives. An early attempt at surface property control can be seen with windshields.

A common issue when driving in rainy weather is obscured vision from built up water on the

windshield. An attempt to alleviate this took the form of commercial products like Rain-X1

which was used to coat the windshield in a thin hydrophobic silicone film. This film, which has

a low surface energy, prevents the water from readily wetting the glass of the windshield and

allows the rainwater to be easily carried away whether by wind or wipers. While rudimentary,

this early step towards control of surface properties in service of a tangible goal underlines a

basic need common to multiple applications in biomedical, solar cell, industrial coating,

microfluidic, and many other industries: the need to control the interaction between solids and

liquids at their interfaces.

Surface wettability is the established quantitative measure of a solid-liquid interfacial

interactions and is governed by the interfacial energy balance described in Young’s Law, shown

below,

𝛾𝑆𝐺 = 𝛾𝑆𝐿 + 𝛾𝐿𝐺 cos 𝜃

where 𝛾𝑆𝐺 is the interfacial energy between the solid surface and the surrounding media, 𝛾𝑆𝐿 is

the interfacial energy between the solid and the liquid droplet, and 𝛾𝐿𝐺 is the interfacial energy

between the liquid droplet and the surrounding media (in air, this is the surface tension). At its’

core, Young’s Law states that the contact angle of a liquid droplet on a solid surface depends

solely on the balance of interfacial energies at the contact line of the droplet as shown in Figure

1.1.1. Essentially, as the interfacial energy of a surface increases, the contact angle decreases. In

this way, the contact angle of a liquid droplet has long been a method with which to measure the

1
surface energy and hence wettability of a surface. Engineering of a surface’s properties involves

changing the surface such that the terms in Young’s Law are modified. Holding the liquid’s

properties constant, these terms are modified through some fundamental change to the surface

itself.

Figure 1.1.1: Schematic Depiction of Young's Law

Up to this point, methods to control surface properties can be classified into two basic

categories: bulk treatments and local patterning. Bulk treatments act on the entire surface to

enact some extreme change in properties, usually making the surface either superhydrophobic or

superhydrophilic (i.e. liquid droplet contact angles greater than 150° or nearly zero,

respectively). This is usually accomplished through chemical/physical vapor deposition

(CVD/PVD) or manipulating the microstructure of the surface. An example of this type of

process would be the silanization2 process frequently used to increase the hydrophobicity of

glass and other solid substrates. This type of treatment is used in various industries for self-

cleaning surfaces, anti-fouling and anti-icing coatings, and painting/coating3. While bulk

treatments are effective in changing the properties of an entire surface, they lack the capability to

spatially control such properties. In many applications, the capability of generating regions on

the same surface with varying surface properties is sought after. One example of such

applications is micro-fluidics, where the liquids need to be confined to a hydrophilic region

surrounded by a hydrophobic surface.

2
 Local patterning employs similar procedures as the bulk treatments, but seeks to generate

localized regions of different surface properties from the remainder of the surface. For instance,

a surface can be made hydrophobic using some bulk salinization process, while local hydrophilic

regions are created in patterns to accomplish some task, such as fabrication of DNA

microarrays4,5. This is typically accomplished through photolithographic or CVD/PVD methods

that make use of masking to achieve the desired patterns. While this approach has been shown to

be useful in the fabrication of micro-optics and micro-fluidics, the inherent design limitation

imposed by a static mask and the high cost associated with the production of this mask greatly

limits the design freedom and capabilities of engineers and researchers that employ these

methods. Additionally, these methods can only produce surfaces which have binary surface

energies. That is, the surface energy at any point on the surface can only be that of the deposited

material or the original substrate. To date, there are no methods which can produce gradients of

surface energy due to these limitations. Thus, there exists an impetus behind the development of

manufacturing methods which can generate both patterns and gradients of surface energy on a

surface through spatially controlled deposition of thin films of material without the need for

expensive masks, and that allow for design and fabrication flexibility. My thesis aims to explore

additive manufacturing as a potential candidate that meets these requirements.

Additive manufacturing (AM) broadly describes any method that utilizes a traveling

energy source and feed material to build the final product or part in a layer by layer fashion.

This fabrication method allows for design choices that would be impossible or cost-prohibitive

using other approaches, such as interior geometry or highly micro-structured surfaces. To date,

using AM for surface property control has not been explored, however methods such as Drop-

3
on-Demand (DOD) inkjet printing allows the production of high spatial resolution patterns of

heterogeneous surface properties through thin film deposition.

My project aims to utilize the design flexibility and intrinsic spatial resolution of AM to

produce distributions of surface properties that would be unachievable through other means. To

this end, the method I utilized involved inkjet printing of dilute polydimethylsiloxane (PDMS)

solutions to form micro-sized, thin hydrophobic films on a glass surface creating a strategic

distribution of surface properties. My hypothesis is that through tuning the concentration of

PDMS in the printing ink and the spatial distribution of the individually deposited PDMS films,

overall surface energy can be controlled. The objective of my thesis work is to test this

hypothesis through experimental and theoretical studies and demonstrate the merit of this

capability through example applications.

This thesis will adhere to the following format. It will explore the background

surrounding production of tailored surface energies, followed by a statement of our research

hypothesis and objectives. The methodology and outcomes of these objectives will then be

discussed followed by a summary that includes my outlook for continuing work on this subject.

4
 SECTION TWO: BACKGROUND

2.1 Surface Property Control

Surface property control is desired in nearly everything. Applications such as improving

solar cell efficiency6, anti-fouling coatings7,8, anti-fogging coatings9,10, and triboelectric energy

harvesting11 are just some examples of the push for extremes in surface properties. Direct

patterning of surface properties is also used in micro-fluidic, micro-optical12,13, and

SOMETHING ELSE.

A specific example in micro-optics illustrates one of the fundamental drawbacks to the

current state of the art regarding spatially-controlled surface property modification. In micro-

optics, lenses are frequently fabricated using individual droplets of liquid, transparent polymers

and the shape of these droplets is what defines the final optical properties. The most common

way to control this shape is by controlling the contact angle. If the contact line is free to move,

then the contact angle can only be changed through manipulation of the surface energy A regular

grid pattern of hydrophilic regions on a hydrophobic surface will both contain the droplet and

increase the contact angle at the hydrophobic/hydrophilic interface. Chen et. al. describe the

patterning of a substrate using a combination of photolithography and spin-coating13. In their

paper, a photoresist is spin coated onto the substrate followed by exposure through a

photolithographic mask. They were successfully able to generate a hydrophobic surface with

localized hydrophilic regions in a grid like pattern. While this led to limited control over their

lens shape, the control was greatly limited by the binary system, i.e. the contact angle was largely

dictated by either the hydrophobic and hydrophilic surfaces. They would have had far greater

control over the contact angle if the specific surface energy of the two surfaces could have been

5
tuned to suit the needs of the design. If this issue is addressed such that the desired shape of the

lens dictated the surface energy, far greater engineering design flexibility would be realized.

2.2 3D Printing

3D printing is an additive manufacturing process in which material is deposited through

some extrusion mechanism in predefined locations to form the desired geometry. A pre-

processing step divides a digital representation of the object into discrete layers that are then

converted into toolpaths for the printer end-effector to follow. 3D printing was first invented in

the 1980’s at MIT and only recently has made its way to mainstream consumers. 3D printing

methods are differentiated by their deposition method. By far the most widespread deposition

method is the extrusion of thermoplastic material known as Fused Deposition Modeling (FDM),

however methods such as stereolithography (SLA), inkjet drop-on-demand (DOD) printing, and

selective laser sintering (SLS) present distinct advantages in areas where FDM fails.

3D printing offers numerous tangible benefits over more traditional manufacturing

methods. The most influential of these is the ability to produce previously unattainable

geometries. In subtractive processes such as milling and EDM, internal structures cannot be

formed. 3D printing also has the capability to deposit different material throughout the print,

which could not be accomplished previously. Additionally, 3D printing generates little waste

compared with traditional subtractive methods, the setup cost of 3D printing is remarkably low

as no tooling is required (as is the case with injection molding), the ability to dictate the

microstructure and surface topography enables a wide variety of additional application spaces,

and the density of a given part can be tailored to a given need.

3D printing has been used in numerous applications including aerospace14,15,

biomedical16, printed electronics17,18, and industry prototyping19. While other methods are

6
categorically better at building three dimensional shapes, inkjet printing is unparalleled in its

ability to create thin films and intricate patterns. Although similar patterns can be generated with

photolithography, these methods require the use of photomasks, the production of which can cost

upwards of $500,00020. The inherent rigidity of the design is also extremely limiting, further

motivating the development of alternative methods.

2.3 Inkjet Printing

Piezoelectric inkjet printing is fundamentally different from other printing methods due

to the discrete nature of the deposition method, i.e. inkjet does not require a backpressure to

dispense and only a small discrete volume will be ejected on each actuation. This discreteness

enables intricate patterning of the deposited material on the print surface. The picoliter volumes

associated with inkjet printing enable spatial resolution comparable to that of stereolithography.

Inkjet printing has been used for a variety of applications. Inkjet printing has been used

to fabricate organic solar cells21–23, micro-optical devices12,13,24–28, printed electronics18,21,29–36,

and others37–39. The common characteristic of these applications is their reliance on the

generation of uniform thin films of material towards some specific purpose. No other additive

manufacturing method can match inkjet printing in this regard.

Although the capabilities of inkjet printing have been exploited in many applications,

including those listed above, the exploration of inkjet printing towards surface property control is

so far unexplored. Research into this area could enable further advancement in the applications

listed above and others such as micro-fluidics.

7
 SECTION THREE: METHODOLOGY AND RESULTS

3.1 Research Hypothesis and Objectives

The method proposed for fabricating surfaces with tailored surface energies and their

characterization is described in Figure 3.1.1. First, dilute solutions of PDMS are printed in a

specified geometry and the solvent is evaporated. Individual droplets are deposited onto the

films and surrounding area to evaluate the surface energy at that location through contact angle

characterization. This information is then used to predict the contact angle of large-scale

droplets. The overarching hypothesis of this project is that through tuning the concentration of

Figure 3.1.1: General Process Schematic

PDMS in the printing ink and the spatial distribution of the individually deposited PDMS films,

overall surface energy can be controlled. To test this hypothesis, inkjet printing capability first

needed to be added to a modular 3D printing system (Objective 1). Thin PDMS films were then

printed using the developed system and the local surface energy was characterized through

contact angle measurement of micro-droplets of a commercial ink called InkOrmo (Objective 2).

The derived surface energies from Objective 2 were used to calibrate a model and predict the

contact angles of large scale lenses using the Cassie-Baxter relationship (Objective 3). Finally,

demonstrations of the usefulness of this method are shown through open-air flow control of a

8
liquid and micro-lens array fabrication (Objective 4). The details of these research objectives are

given below.

3.2 Objective 1: Integration of Inkjet Printing Capability with a Direct-Write Print System

Vital to any printing task is the printer itself. As such, the development of the custom

printer used in this work was the first important task undertaken towards the investigation of the

hypothesis. The printing in this thesis was accomplished using the Manufacturing Processes and

Figure 3.2.1: Inkjet Printing System

Machinery Laboratory’s custom printing system, pictured in Figure 3.2.1. This system consists

of three orthogonal motion stages (i.e XYZ stages), and a deposition head. A MicroFab inkjet

printhead and an Nscrypt direct write printhead were used for the PDMS film and lens

deposition, respectively. The stages and printhead control electronics were controlled using a

LabVIEW interface. This interface translated input commands to the respective languages of the

integrated controls to execute synchronized movement and deposition. It does this by reading in

custom G-Code files that specify what action to take using three letter commands. A sample G-

Code file is outlined below:

9
 GO2 34 5 21.75 50 Sends the stages to a specific XYZ location
SET mode cont Sets the inkjet controller to “continuous” print mode
TRI Triggers the deposition
WAI 3000 Waits for 3000ms
STP Stops printing
GO2 -77.75 15 -28.25 50 Sends the stages to the “park” location
A custom G-Code file like the one above is stored by the LabVIEW program which then

executes each line sequentially. For some of the hardware, such as the Aerotech stages, existing

LabVIEW VIs were used to accomplish the given task. Other hardware, such as the MicroFab

inkjet system, required custom VI files to be written to accomplish the prescribed task. A VI

Figure 3.2.2: LabVIEW VI for Changing Trigger Mode

was written to manipulate every aspect of jetting. A sample VI is included in Figure 3.2.2. This

VI was used to control the jetting mode of the MicroFab controller (i.e. continuous or discrete).

The inkjet printing head itself uses piezoelectric actuation. The inkjet printing head is a slender

glass tube coated in a piezoelectric material. When a positive voltage is applied, the glass tube

expands radially and contracts axially. This motion induces a negative (expansive) pressure

wave in the fluid which propagates along the tube in both directions simultaneously. The wave

reflects as a positive (compressive) pressure wave at the reservoir end of the tip and propagates

10
 Figure 3.2.3: Basic Inkjet Dispensing Printhead
http://www.microfab.com/a-basic-ink-jet-microdispensing-setup/basicsetup-ink-jet-microdispenser

back to the orifice. The localized positive pressure displaces the fluid boundary far enough that

the surface tension effects of the fluid allow the newly formed droplet to separate from the bulk.

A schematic of an inkjet printhead and evolution of a printed droplet is shown in Figure 3.2.3.

These figures are provided by the producer of our printhead, MicroFab Technologies. A typical

waveform is bipolar trapezoidal as shown in Figure 3.2.4. The nine numbers that describe the

waveform and their effect on droplet jetting is described below:

Rise Time

The first rise time dictates how fast the dwell voltage is reached. A shorter rise time

essentially equates to a higher impulse imparted onto the fluid. This is important for

higher viscosity liquids as the pressure wave amplitude will decrease faster.

11
 Figure 3.2.4: Typical Waveform used in Inkjet Printing

Dwell Voltage

The dwell voltage is the initial (usually) positive voltage applied to the dispensing tip and

is the most vital component of the waveform. The magnitude of the deflection of the

glass tube is directly proportional to this value, and tuning of this parameter is required

for stable jetting of a given fluid. Intuitively, higher viscosity liquids require a higher

dwell voltage.

Dwell Time

Dwell time is the length of time spent at the dwell voltage by the tip. While the main

factor that dictates the size of the printed droplet is the diameter of the orifice, this

parameter can be tuned to limit the amount of material jetted. Frequently with low

viscosity liquids, a long dwell time will result in multiple droplets per waveform which is

combated through careful manipulation of this parameter.

12
Fall Time

Formation of satellite droplets is a persistent obstacle to stable inkjet printing and the fall

time is critical in the management of these droplets. Extending the fall time allows for a

slower separation of the printed drop from the bulk which, in turn, decreases the chance

for formation of a satellite droplet.

Echo Voltage

The echo voltage defines the 2nd voltage peak of the waveform. In a simple trapezoidal

waveform this is set to zero, but setting a negatively echo voltage can help droplet

separation when it proves difficult to separate.

Echo Time

Echo Time dictates the length of time the waveform spends at the echo voltage.

Lengthening this time will

Idle Voltage

The idle voltage is the baseline voltage the tip is kept at when not executing the current

waveform. For my experiments, this was set to zero.

Rise Time 2

This is the amount of time it takes to rise from the echo voltage to idle voltage. It has an

insignificant effect on jetting and as such was kept constant during my experiments.

Frequency

The frequency dictates how many droplet cycles are executed per second. The control

electronics generate a waveform such that the number of cycles are equally spaced

throughout each second.

13
 A common issue associated with inkjet printing is what is known as the “first drop

problem”. Local evaporation increases the ink concentration and, by extension, the ink viscosity

at the tip orifice. This increase in viscosity inhibits stable droplet production and necessitates

mitigation strategies. One such strategy is to simply wipe the orifice of the tip with a swab.

Another, less reliable, strategy is to use a “purge” waveform that imparts significantly more

energy to the ink. This allows the ink to “break through” the meniscus formed by the higher

viscosity ink at the tip. Table 3.2.X gives the optimal waveform numbers used for printing in

this thesis.

Ink Material Rise Dwell Dwell Fall Echo Echo Idle Rise Freq.

Time Voltage Time Time Voltage Time Voltage Time 2

(μs) (V) (μs) (μs) (V) (μs) (V) (μs) (Hz)

PDMS/HEPTANE 4 12 9 4 -9 50 0 3 Varies

INKORMO 3 45 6 3 0 50 0 3 Varies

Table 1: Optimal Waveform Parameters

3.3 Objective 2: Characterization of the Local Surface Properties of the Printed Films

In this objective, solutions of PDMS were inkjet printed onto a glass surface and then

characterized. The inks used for film deposition were prepared through sequential dilution of

PDMS with heptane. PDMS part A and B are first mixed at a 10:1 ratio in a centrifugal mixer.

The mixed PDMS is then mechanically mixed with heptane to create a 10 wt% mixture. This ink

is then further diluted with additional heptane to create .5, 1, and 2 wt% mixtures. These

mixtures were inkjet printed such that individual films could be tested. This testing was

performed through contact deposition for contact angle evaluation, pendant drop testing for

InkOrmo’s surface tension, and AFM work of adhesion characterization. These steps are

described in detail below.

14
Contact Deposition

To determine the contact angle, and therefore the wetting properties, of a small

subsection of the substrate surface, small volumes of a micro-optic ink called InkOrmo were

deposited onto the surface. Initially, this deposition was attempted through inkjet printing, but

the droplets could not be printed onto the films reliably and so an alternative deposition method

was used for this purpose.

To mitigate the positioning inaccuracy, a method in which ink was deposited on the

surface through capillary action was developed. A glass tip created using a pipette puller was

filled with InkOromo. The weight of the ink caused a small meniscus of ink to form at the

orifice of the glass tip. This meniscus was then brought into contact with the surface at a

specified location. Capillary action caused the ink to wet the surface at the specified location

and, when the tip was moved away, left a small droplet in the desired location.

To ensure the droplet was placed in the correct location, I employed a Keyence laser

scanner. I would first deposit a droplet in an arbitrary location on the substrate using the contact

method described above. I would then locate this droplet using the laser scanner and calculate

the difference between the stage position during deposition and the stage position when aligned

with the laser scanner. I would then align the scanner with a film on which I wanted to deposit a

droplet. I would then move the stages back to the tip position using the calculated difference and

deposit the lens in the desired location. I automated this task using a LabVIEW VI called “Delta

Assist”. The block diagram is shown below in Figure 3.3.1.

15
 Figure 3.3.1: Delta Assist LabVIEW VI

An array of droplets deposited in this fashion is shown in Figure 3.3.2. The droplets

deposited in this way have diameters of less than 50 µm and therefore are useful for extracting

the surface energy at locations on and around the deposited film. To determine the contact angle

of an individual droplet, a combination of methods was employed. The surface profile was

captured using a Zygo profilometer. Frequently, the profilometer was not able to capture data

near the edge of the deposited droplet due to the high contact angle and resulting refraction. The

16
profile shows 12 droplets deposited through the contact method surrounding a printed one

percent thin film of PDMS. The orange rings that define most of the droplets indicates a lack of

data. The profilometry data shows the droplet as a pillar when we know from microscopy that

this is not true. This discrepancy necessitated the development of a MATLAB code to

approximate the droplet shape in these regions as well as the contact angles of the droplets.

Figure 3.3.2: Small Scale Droplets

The MATLAB code I generated is a basic optimization algorithm. I first manually crop

out the top of the droplet and threshold the image such that only the actual data is included. I

then run this data through my optimization algorithm. The code generates a vector of XYZ data

for pixel of an associated droplet that we know to be a real value, then optimizes the location of

the center of a sphere based on the standard deviation of the distances of each point to that

center. Essentially, when the sphere of best fit is found, this standard deviation will be

minimized. This model sphere is then used to calculate the angle with the horizontal based on

the max height of the droplet in question. The contact angles calculated in this way have been

17
 50

45

40

35
Contact Angle (°)

30

25
y = -9.5761389697x2 + 31.3567835182x + 19.4651807152
20 R² = 0.9624394403

15

10

0
0 0.5 1 1.5 2
Concentration (%)
Figure 3.3.3: Contact Angle vs. PDMS Concentration
plotted against film concentration in Figure 3.3.3. Each point in this plot represents the average

contact angle of droplets deposited on to a single discrete film. The fitted model is a second

order polynomial with an r-squared value of .962.

While this data quantifies the contact angle relationship with PDMS concentration, it

only gives us information about the surface properties if the surface is ideal and adheres to

Young’s Law. If the small-scale droplets deposited using the touch method are significantly

influenced by pinning or the roughness of the surface, the validity of this data for surface

property analysis is questionable. This motivated the exploration of contact angle validation

through work of adhesion analysis.

Atomic Force Microscopy/Work of Adhesion

The work of adhesion describes the work required to separate two materials in contact41,42

and is governed by the following equation:

𝑊𝑎𝑑
= 𝛾𝑆𝐺 + 𝛾𝐿𝐺 − 𝛾𝑆𝐿
𝐴

18
Where A is the surface area in contact. Combining this equation with Young’s Law from above,

we arrive at:

𝑊𝑎𝑑
= 𝛾𝐿𝐺 (1 + cos 𝜃)
𝐴

Therefore, if the work of adhesion on a substrate is known, it is possible to predict the

contact angle of a liquid with known surface tension. Additionally, this equation can be used to

generate an expected contact angle to check against experimental contact angles to probe for any

non-ideality in the printing surface (i.e. check to see if it obeys Young’s Law). The work of

adhesion was measured using a variation on an atomic force microscopy (AFM) measurement

technique previously employed by Burnham et. al.43 AFM is a measurement method that

correlates the deflection of a small cantilever probe to surface properties such as height,

adhesion, and surface deformation. Figure 3.3.4 (top) shows a typical force curve generated by

an atomic force microscope. The blue curve corresponds to the force on the tip during its

approach to the surface, while the red curve describes the force on the tip during retraction. The

area in the negative region of the retraction curve is the work of adhesion. The length of the

retraction curve while the adhesive force is acting on the tip is called the separation. Figure

3.3.4 (bottom) shows the retract portions of the force curves on glass and a PDMS film. The

work of adhesion is lower on the PDMS film.

To obtain the work of adhesion between InkOrmo and a PDMS film, I first coated the

AFM tip in InkOrmo by submerging the tip in a large droplet of InkOrmo. I then obtain a force

curve on an area of the substrate with a known contact angle, i.e. bare glass. A schematic of the

coated tip during retraction is shown in Figure 3.3.5. The work of adhesion from the area with a

19
 Figure 3.3.4: AFM Force Curves

known contact angle is used to find the volume of the ink coating the tip using the following

equation:

2√𝜋𝐴ℎ2
𝑉 = 2ℎ𝐴 − (𝜋 − 2𝜃 − sin(𝜋 − 2𝜃))
cos 2 𝜃

where A is the surface area covered by the ink. I then obtained a force curve on a PDMS thin

film. Using the work of adhesion and separation from this force curve, and knowing the volume

20
of the ink coating the tip must be conserved, I ran an optimization code that solved for the

theoretical contact angle of the ink on the PDMS film which satisfied these conditions. This

contact angle prediction for the two percent PDMS films is 46°. The agreement of the calculated

contact angles and the theoretical predictions using Young’s Law and the work of adhesion tells

us that neither the roughness of the surface nor pinning significantly impact the wetting

characteristics of the droplets and that the calculated contact angles from the contact deposition

method can be utilized for surface property predictions.

In addition to the contact angles of these small-scale droplets, information about the films

themselves were recorded. Consistent with other dilute solutions, the deposited films exhibited

the “coffee-ring effect”. The “coffee-ring” effect is a phenomenon that describes the final

distribution of solute on a solid surface due to the flow within an evaporating droplet of solution.

The diverging evaporative flux approaching the edge of the droplet causes capillary flow of

liquid from inside the droplet to move outwards towards the edge to replace the liquid that has

Figure 3.3.5: Schematic of Coated AFM Tip During Separation

21
been lost to evaporation44. This outward flow causes an increase in solute concentration near the

edge which results in pinning of the droplet contact line preventing this line to move inwards and

producing the familiar “coffee-ring” buildup of solute material in a ring formation. Data on the

film roughness, thickness in the center, height of the coffee ring, and profiles for the various

concentrations are shown in Figure 3.3.6.

While taking the concentration versus contact angle data, I noticed an odd trend. The

contact angle of droplets placed in the immediate vicinity of the deposited film also exhibited

higher than expected contact angles that decreased with increasing distance from the film.

Closer inspection was carried out and the following data was obtained in the region surrounding

a two percent PDMS film. This data is shown in Figure 3.3.7. The orange line in the plot

indicates the contact angle of bare glass.

35 0.01
Center Thickness (nm)

30 0.008
25
Ra (nm)

20 0.006
15 0.004
10
5 0.002
0 0
0.5 1 2 0.5 1 2
PDMS Concentration (%) PDMS Concentration (%)

200 0.01
Coffee-Ring Height

150 0.008
Rms (nm)

0.006
(nm)

100
0.004
50 0.002
0 0
0.5 1 2 0.5 1 2
PDMS Concentration (%) PDMS Concentration (%)

Figure 3.3.6: PDMS Film Characteristics

What we deemed to be the “halo effect” can be attributed to the evolution of the droplet

shape as it impacts the surface. The droplet initially spreads out until the kinetic energy of the

22
droplet has been dissipated. At this point the surface tension of the droplet acts to pull the

droplet back into a hemispherical shape. It appears that an extremely thin, non-visible layer of

PDMS is left behind during this retraction, which manifests as a decrease in surface energy when

compared with the bare glass substrate. While this retraction is taking place, higher evaporation

rate near the edge of the droplet is driving capillary flow of ink towards the droplet edge which

eventually pins the edge resulting in the visible coffee-ring left by every film drop. This halo

effect needs to be accounted for when designing surface energy distributions in Objective 3.

In summary, the films were found to have increasing roughness as concentration

increased. The surface energy of the deposited film also increased as the concentration was

increased. The so-called “halo effect” surrounding the deposited film was also quantified. The

next step is to use this information to tune the large-scale surface energy.

50

45

40
y = 0.0000738612x2 - 0.0898546074x + 45.8293214745
35 R² = 0.9856551912
Contact Angle (°)

30

25

20

15

10

0
0 100 200 300 400 500 600 700 800
Radial Distance From Film Center (μm)

Figure 3.3.7: The Halo Effect

23
Pendant Drop Test

The pendant drop test is a facile approach to determining the interfacial tension between a

liquid and gas. A droplet of liquid is suspended from a nozzle and the profile is examined. This

profile is dictated by the balance between gravity and the surface forces which can be described

by the differential equation40

1 sin 𝜙 z
+ = −Β + 2
𝑅/𝑅𝑎 𝑥/𝑅𝑎 Ra

Where Β is defined as

𝑅𝑎2 𝑔Δ𝜌
Β=
𝛾

Wherein Δ𝜌 is the difference in densities of the liquid and the surrounding atmosphere, 𝑔 is the

acceleration due to gravity, 𝑅𝑎 is the radius of curvature at the apex of the drop, and 𝛾 is the

interfacial tension. Arashiro et. al. described an empirical relationship for the Β as a function of

𝑆,

2 +9.92425𝑆 3 −2.585035𝑆 4
𝛣 = √𝑒 −6.70905+15.30025𝑆−16.44709𝑆

where

𝐷𝑒
𝑆=
𝐷𝑠

And De and Ds are the widest diameter of the drop and the diameter of the drop at a vertical

distance of De away from the apex of the drop, respectively. Utilizing the equations above, the

interfacial tension (i.e. surface tension) can be solved for directly. Figure 3.3.1 shows the image

used in determining the surface tension of InkOrmo (our test liquid). The surface tension of

InkOrmo was found to be 24.09 mN/m.

24
 Figure 3.3.1: Pendant Drop Image used for Surface Tension Measurement

3.4 Objective 3: Utilization of Small Scale Property Control for Large Scale Property

Control

Once the small-scale surface energy distributions were clearly understood, the next step

in the process was the tailoring of wetting characteristics of a large-scale area. To accomplish

this, regular grids of two percent films were printed, and large volume droplets were inkjet-

printed on the grids to determine the surface energy properties over a large area. A useful

relationship for quantification of the surface energy of a heterogeneous surface is the Cassie-

Baxter equation45 shown below:

∑ 𝑓𝑖 cos 𝜃𝑖 = cos 𝜃
𝑖

25
 Figure 3.4.1: Cassie-Baxter Equation for Wetting Angle
Seo et. al.

In this equation, 𝑓𝑖 is the area fraction associated with the regions of the surface

that exhibit contact angle 𝜃𝑖 . In Figure 3.4.1 a schematic representation of this is shown with

two surface energies. In this project, the two regions in this schematic are the thin PDMS films

and the bare glass.

Two models were developed to predict the contact angle of a large scale printed droplet.

Each model examined a unit cell of the printed pattern. This unit cell is repeated throughout the

entire pattern and therefore the surface energy of that cell corresponds to the surface energy of

the entire substrate. The formulation of the unit cell used for the non-halo predictions is shown

in Figure 3.4.2. The plots on the right show the contact angle (top) and cosine of the contact

angle (bottom) used in the Cassie-Baxter equation. The diameter of a printed two percent film

was found through inspection to be 150 µm.

The first model ignores the effect of the halo and only utilizes the coffee-ring area in the

Cassie-Baxter equation. The second model was developed in MATLAB using the halo effect

results from the previous subsection. A discretized distribution of contact angle in the unit cell

for each pattern was developed using the results from the previous section. The product of the

energy and its associated area was summed for the entire area and then divided by the total area

giving a surface energy value for the unit cell. This surface energy value was then converted

26
back into contact angle for the predictions shown in Figure 3.4.2. The green markers indicate the

prediction when the halo effect is ignored. The orange markers correspond to the predictions

that include the halo effect. It is easy to see that the inclusion of the halo effect is vital to an

accurate model.

Figure 3.4.2: Model Unit Cell Models

50
45
40
35
Contact Angle

30
25
20
15
10
5
0
100 200 400 800 1600
Pitch (microns)
Experimental Halo Predictions Non-Halo Predictions

Figure 3.4.3: Predicted and Experimental Large-Scale Contact Angles

27
 The experimental results deviate substantially from the model predictions. This is likely

because as overlapping films are deposited, some reorganization of previously deposited films

takes place. This will change the distribution of surface energy on the surface rendering the halo

effect model somewhat inadequate. Also, as the pitch approaches the diameter of the large-scale

lenses, uniform contact of the lenses with the PDMS films can no longer be guaranteed which

will skew the experimental lens contact angles downwards. Images of the large-scale lenses are

shown in Figure 3.4.4.

Figure 3.4.4: Large Scale Lens Images

28
3.5 Objective 4: Demonstration of the Method in Flow Control and Micro-Lens Array

Fabrication

One application of this work is in the production of patterned surface energies for low-

cost, facile micro-fluidics. Towards this end, I have printed a simple demonstration for guiding

the flow of a liquid droplet on a glass substrate. Figure 3.5.1 shows the printed pattern along with

the controlled flow of a droplet mixed with a green dye. The pattern was designed in CAD

software and printed using two percent PDMS ink.

This demonstration shows the ability of this method to generate “pathways” of surface

properties conducive towards microfluidics. As this research progresses, inclusion of branching

points wherein gradients of surface energy can direct the flow of the droplet based on its’ own

surface tension will increase the usefulness of the method.

Another demonstration of this technique was explored in the fabrication of simple micro-

lens arrays. In Figure 3.5.2, printed lenses are shown at two different focal lengths along with

Figure 3.5.1: Printed Micro-Fluidic Device

29
microscopy images of that same array. Figure 3.5.2 also shows the distribution of focal lengths

with changing concentrations of PDMS printing ink and microscopy images of the change in lens

shape with a change in concentration. While the results showed wide variation at each film

concentration, further refinement of this method could enable higher quality micro-lens array

production.

Figure 3.5.2: Micro-Lens Array Fabrication

30
 SECTION FOUR: CONCLUSION

This thesis has shown the capability of a novel inkjet printing method towards tailoring

the surface energy of a substrate. A custom inkjet printing system was developed to accomplish

the research objectives by integrating discrete hardware into a single system using a LabVIEW

interface. This system was used to print dilute solutions of a hydrophobic polymer PDMS to

generate thin films. These films exhibited localized hydrophobicity that varied with the

concentration of PDMS in the printing ink and the spatial distribution of the films. The surface

energy of these films was characterized using a contact deposition method and profilometry.

These localized surface energy values were used to generate predictions for large-scale wetting

characteristics. This method was then utilized to fabricate micro-lens arrays and an open air

micro-fluidic device.

To progress the research in the future, I suggest a few tests. First, addition of a surfactant

to the printing ink might stabilize the droplet and aid in more uniform film deposition which may

mitigate the halo effect seen in these studies. Additionally, further investigation is warranted

into the surface properties of overlapping films to gain more insight into the reorganization of the

PDMS film.

31
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