Analysis of Colloidal Pigment Aggregation and Ink Media Interactions in Porous Medial

ANALYSIS OF COLLOIDAL PIGMENT
AGGREGATION AND INK MEDIA

INTERACTIONS IN POROUS MEDIA

by

Karthik Thirukonda Viswanath
May 09, 2012

A thesis submitted to the
Faculty of the Graduate School of
the University at Buffalo, State University of New York
in partial fulfillment of the requirements for the
degree of

Master of Science

Department of Chemical and Biological Engineering

ACKNOWLEDGEMENTS

I would like to use this opportunity to thank my dad, mom and friends without
whose help this work would have not been possible.

I would like to thank Dr. Edward Furlani for his support and guidance over the
past several months. I would also like to thank Dr. Mark Swihart and the
Chemical Engineering faculty at UB for their support in my endeavors.

I would like to thank cabot corp. for their support in this project.

Table of contents

ABSTRACT ..1
1 INTRODUCTION .................................................................................... 3
2 THEORY ................................................................................................. 4
2.1 Introduction .................................................................................................... 4
2.2 Ink Pigments .................................................................................................. 4
2.3 Paper .............................................................................................................. 6
2.4 Surface Tension ............................................................................................. 9
2.5 Capillary Pressure ........................................................................................ 11
2.6 Viscosity ...................................................................................................... 13
2.7 Contact Angle .............................................................................................. 14
2.8 Porosity, Permeability and Drag Coefficient ............................................... 16
2.9 Navier Stokes Equation............................................................................. 18
2.10 Colloidal Particles ........................................................................................ 21
2.11 Surface Charge ............................................................................................. 22
2.12 Gouy Chapman Model .............................................................................. 23
2.13 Electrophoretic Mobility and Zeta Potential ................................................ 27
2.14 Aggregation.................................................................................................. 27
2.15 Model Collision Rates.................................................................................. 29
2.16 Perikinetic Collision Mechanism ................................................................. 30
2.17 Orthokinetic Collision and Differential Settling Mechanism ...................... 32
2.18 Comparison of Rates .................................................................................... 34
2.19 Stability Ratio for Perikinetic Collision ....................................................... 36
2.20 Interparticle Forces ...................................................................................... 36
2.21 Electrostatic Repulsive Force ...................................................................... 37
2.22 Van der Waals .............................................................................................. 38
2.22.1 Other interparticle forces ..................................................................... 40
3 FLUIDIC ANALYSIS AND MATHEMATICAL MODELING ...................42
3.1 Introduction .................................................................................................. 42
3.2 Capillary Pressure ........................................................................................ 42
3.3 Interparticle Forces ...................................................................................... 43
3.4 Van der Waals Attractive Potential.............................................................. 44
3.5 Electrostatic Repulsive Potential ................................................................. 45
Table of contents

3.6 Poisson Boltzmann Equation in Linearized form ........................................ 46
3.7 Collision Mechanism ................................................................................... 47
3.8 Perikinetic Stability Ratio ............................................................................ 50
3.9 Aggregation Coefficient............................................................................... 51
3.10 Population Balance Equation ....................................................................... 53
3.11 Discretization Pattern ................................................................................... 54
4 RESULTS ..............................................................................................58
4.1 Introduction .................................................................................................. 58
4.2 Simulation .................................................................................................... 58
4.2.1 Example 1 ............................................................................................ 59
4.2.2 Example 2 ............................................................................................ 60
4.2.3 Example 3 ............................................................................................ 62
4.2.4 Comparison of results .......................................................................... 65
4.2.5 Time versus Surface Tension plots ...................................................... 65
4.2.6 Width versus Surface Tension plots .................................................... 66
4.2.7 Height versus Surface Tension plots.................................................... 67
4.3 Mathematical Model .................................................................................... 67
4.3.1 Example 1 ............................................................................................ 67
4.3.2 Example 2 ............................................................................................ 68
4.4 Comparison between particle aggregation in NaCl and CaCl
2
.................... 70
5 Appendix ..............................................................................................73
5.1 Time, Width and Height .............................................................................. 73
References 75
List of figures

Figure 2-1 Range of electromagnetic spectrum ............................................................. 5
Figure 2-2 (a) SEM Image of Ink on porous media (b) Schematic representation of ink
media absorption ............................................................................................................ 8
Figure 2-3 The Gouy - Chapman Model...................................................................... 25
Figure 2-4 Potential Profile for Gouy-Chapman Model .............................................. 25
Figure 2-5 Perikinetic Collision Mechanism ............................................................... 30
Figure 2-6 Orthokinetic Collision Mechanism ............................................................ 33
Figure 2-7 Interaction energy of colloidal particle ...................................................... 37
Figure 3-1 Two dissimilar spheres ............................................................................... 44
Figure 3-2 Potential Energy of interaction between particles of dissimilar radii ........ 45
Figure 3-3 Interaction Energy using DLVO theory ..................................................... 47
Figure 3-4 Perikinetic collision for different particle size ........................................... 48
Figure 3-5 Orthokinetic collision for different particle size ........................................ 49
Figure 3-6 Differential Settling for different particle size ........................................... 49
Figure 3-7 Stability ratio for perikinetic collision mechanism .................................... 51
Figure 3-8 Aggregation coefficient for different particle size ..................................... 52
Figure 3-9 Particle Concentration as function of discretized particle volume ............. 54
Figure 3-10 Flow chart for mathematical modeling .................................................... 57
Figure 4-1 (a) 6.5pl drop at time = 0 (b) drop hitting the porous surface at 12.5 m/s 59
Figure 4-2 6.5pl droplet after steady state ................................................................... 60
Figure 4-3 (a) 10pl drop at velocity 12.5 m/s (b) after hits the surface ....................... 61
Figure 4-4 drop after steady state ................................................................................. 62
Figure 4-5 (a) 3pl drop hitting at 5 m/s (b) after hitting the surface ............................ 63
Figure 4-6 Drop after steady state ................................................................................ 64
Figure 4-7 Time vs. Surface tension for various volume of droplet ............................ 65
Figure 4-8 Time vs. Surface tension for various viscosities ........................................ 65
Figure 4-9 Time vs. Surface tension for various pore diameter .................................. 66
Figure 4-10 Width vs. Surface tension for various volume of droplet ........................ 66
Figure 4-11Height vs. Surface tension for various volume of droplet ........................ 67
Figure 4-12 Particle Number vs. time for valency = 1 ................................................ 68
Figure 4-13 Particle Number vs Time for valency = 2 ................................................ 69
List of tables

Table 1 various parameters used for the study ........................................................... 58
Table 2 Input variables for example 1........................................................................ 59
Table 3 Output values for example 1 ......................................................................... 60
Table 8 various input and output values for 3pl ......................................................... 73
Table 9 various input and output values for 6.5pl ...................................................... 74
Table 10 various input and output values for 10pl ..................................................... 75

1

ABSTARCT
The commercialization of a modern inkjet printing system is a complex undertaking
that requires an interdisciplinary team to address numerous critical and fundamental
issues encountered throughout the product development cycle. An inkjet
development effort spans a broad range of diverse yet coupled activities that include
the rational design of ink formulations, design and optimization of a droplet
generator, precision control of a high-throughput deposition of droplets onto a
moving media and modeling and characterization of various ink media interactions,
e.g. spreading, absorption and coalescence of droplets, to achieve high image quality.
The focus of this dissertation is on ink media interactions, which directly impact
inkjet print quality and speed. We present and demonstrate two models for predicting
ink media interactions, a CFD-based approach for predicting the absorption and
spreading of droplets upon impact with porous media, and a population balance
approach for predicting the flocculation of colloidal ink pigments during the ink
deposition process. The CFD analysis takes into account the physical properties of
the media such as porosity, permeability and contact, and critical properties of the
ink including surface tension and viscosity, as well as the size and velocity of the
incident droplet. The population balance model, which is based on Smoluchowski
kinetics and DLVO theory, is used to predict the flocculation of ink pigments taking
into account the initial size distribution and surface potential of the particles and the
ionic strength of the ink. Theoretical and experimental results are presented to
quantify these processes. The challenges associated with the quantifying ink media
interactions are also discussed.

2

A study is presented of various effects involved in the interactions of pigmented ink
with porous media in conventional inkjet printing applications. The study involves
the use of two different numerical models, one for predicting the absorption of ink in
porous media and another for predicting the flocculation of pigment during
absorption. Specifically, computational fluid dynamic (CFD) analysis is used to
predict the absorption of an impacting droplet on a porous substrate taking into
account the velocity, viscosity and surface tension of the droplet and the porosity and
permeability of the media. A population balance model is used to study flocculation
of pigments. The models are demonstrated via application to conventional inks and
media.

3

1 INTRODUCTION

Printing ink is a $10 billion global industry and Inkjet printing has seen lot of
development over the years which have made the printing cheap, fast and accessible.
But we would like to have ultrafast printing with great accuracy and to make it
possible we have to understand and study the ink media interactions while printing.
Pigments in ink plays a vital role in print quality and cost, therefore carbon black is
replaced with dyes. Black ink is made using carbon black. And white pigments, such
as titanium dioxide, are used either by themselves or to adjust characteristics of color
inks. Inks also contain additives such as waxes, lubricants, surfactants, and drying
agents to aid printing and to impart any desired special characteristics. Pigment based
inkjet inks have assumed leading market positions in desktop as well as wide-format
inkjet printing since they provide outstanding light and water fastness as well as
superior optical densities.

4

2 THEORY

2.1 Introduction
This chapter describes the necessary background topics required to understand the
theory of mathematical model for flocculation and ink absorption in media. The first
section describes the factors that play important role during ink absorption. The next
few sections describe basic properties of colloidal particles, aggregation kinetics,
collision mechanisms, particle stability, and aggregate structure. The attractive and
repulsive forces, such as electrostatic repulsive and van der Waals attractive forces,
will then be discussed. Next, a mathematical introduction to the population balance
model is included. The theory presented in this chapter introduces the basic concepts
necessary to understand the ink media interactions.

2.2 Ink Pigments
A pigment is a material that changes the color of reflected or transmitted light as the
result of wavelength-selective absorption. This physical process differs from
fluorescence, phosphorescence, and other forms of luminescence, in which a material
emits light. Pigments appear the colors they are because they selectively reflect and
absorb certain wavelengths of visible light. White light is a roughly equal mixture of
the entire spectrum of visible light with a wavelength in a range from about 380 or
400 nanometers to about 760 or 780 nm. When this light encounters a pigment, parts
of the spectrum are absorbed by the chemical bonds of conjugated systems and other
components of the pigment. Some other wavelengths or parts of the spectrum are
reflected or scattered. Most pigments are charge-transfer complexes, like transition

5

metal compounds, with broad absorption bands that subtract most of the colors of the
incident white light. The new reflected light spectrum creates the appearance of a
color. Ultramarine reflects blue light, and absorbs other colors. Pigments, unlike
fluorescent or phosphorescent substances, can only subtract wavelengths from the
source light, never add new ones.

The appearance of pigments is intimately connected to the color of the source light.
Sunlight has a high color temperature, and a fairly uniform spectrum, and is
considered a standard for white light. Artificial light sources tend to have great peaks
in some parts of their spectrum, and deep valleys in others. Viewed under these
conditions, pigments will appear different colors.

Figure 2-1 Range of electromagnetic spectrum

Other properties of a color, such as its saturation or lightness, may be determined by
the other substances that accompany pigments. Binders and fillers added to pure
pigment chemicals also have their own reflection and absorption patterns, which can
affect the final spectrum. Likewise, in pigment/binder mixtures, individual rays of
light may not encounter pigment molecules, and may be reflected as is. These stray

6

rays of source light contribute to the saturation of the color. Pure pigment allows
very little white light to escape, producing a highly saturated color. A small quantity
of pigment mixed with a lot of white binder, however, will appear de-saturated and
pale, due to the high quantity of escaping white light.

Carbon black (Color, PBK-7) is the name of a common black pigment, traditionally
produced from charring organic materials such as wood or bone. It appears black
because it reflects very little light in the visible part of the spectrum, with an albedo
near zero. The actual albedo varies dependent upon the source material and method
of production. It is known by a variety of names, each of which reflects a traditional
method for producing carbon black:
- Ivory black was traditionally produced by charring ivory or bones.
- Vine black was traditionally produced by charring desiccated grape vines and
stems.
Newer methods of producing carbon black have superseded these traditional sources,
although some materials are still produced using traditional methods. For commercial
purposes, it is very useful. The inks industries prefer grades of carbon black that are
acid oxidized. Acid is sprayed in high temperature dryers during the manufacturing
process to change the inherent surface chemistry of the black. The amount of
chemically-bonded oxygen on the surface area of the black is increased to enhance
performance characteristics.

2.3 Paper
Ink requirement is defined as the amount of ink needed to print a unit area with a
standard Solid Ink Density. Different paper substrates require different amount of ink

7

to achieve the standard SID. A highly porous substrate generally requires higher
amount of ink compared to a less porous substrate. Therefore, to study the ink
mileage of different paper substrates, this test can be done on all the newsprint
samples. Ink requirement also depends upon the ink formulation and the color
strength of the pigments. From this test, the ink mileage of all the four process
colors, when printed in the same paper, can be studied.

Because paper is composed of a randomly felted layer of fiber, it follows that the
structure has a varying degree of porosity. Thus, the ability of fluids, both liquid and
gaseous, to penetrate the structure of paper becomes a property that is both highly
significant to the use of paper. Paper is a highly porous material and contains as
much as 70% air. Porosity is a highly critical factor in printing papers laminating
paper, filter paper, cigarette Paper, bag paper, anti-tarnish paper and label paper.
Porosity is the measurement of the total connecting air voids, both vertical and
horizontal, that exists in a sheet. Porosity of sheet is an indication of absorptivity or
the ability of the sheets to accept ink or water. Porosity can also be a factor in a
vacuum feeding operation on a printing press.

8

Figure 2-2 (a) SEM Image of Ink on porous media (b) Schematic representation
of ink media absorption

Air Resistance method is the resistance to the passage of air, offered by the paper
structure, when a pressure difference exist between two sides of paper. It is measured
as the time for a given volume of air to flow through a specimen under specified
conditions. Air resistance is indirect indicator of degree of beating, compaction of
fibers and type and amount of fillers.

9

2.4 Surface Tension
Surface tension is a property of the surface of a liquid that allows it to resist an
external force. This property is caused by cohesion of similar molecules, and is
responsible for many of the behaviors of liquids. Surface tension has the dimension
of force per unit length or of energy per unit area. The cohesive forces among liquid
molecules are responsible for the phenomenon of surface tension. In the bulk of the
liquid, each molecule is pulled equally in every direction by neighboring liquid
molecules, resulting in a net force of zero. The molecules at the surface do not have
other molecules on all sides of them and therefore are pulled inwards. This creates
some internal pressure and forces liquid surfaces to contract to the minimal area.

Surface tension is responsible for the shape of liquid droplets. Although easily
deformed, droplets of water tend to be pulled into a spherical shape by the cohesive
forces of the surface layer. In the absence of other forces, including gravity, drops of
virtually all liquids would be perfectly spherical. The spherical shape minimizes the
necessary "wall tension" of the surface layer according to Laplace's law.

Another way to view surface tension is in terms of energy. A molecule in contact
with a neighbor is in a lower state of energy than if it were alone (not in contact with
a neighbor). The interior molecules have as many neighbors as they can possibly
have, but the boundary molecules are missing neighbors (compared to interior
molecules) and therefore have a higher energy. For the liquid to minimize its energy
state, the number of higher energy boundary molecules must be minimized. The
minimized quantity of boundary molecules results in a minimized surface area.

10

As a result of surface area minimization, a surface will assume the smoothest shape it
can (mathematical proof that "smooth" shapes minimize surface area relies on use of
the EulerLagrange equation). Since any curvature in the surface shape results in
greater area, a higher energy will also result. Consequently the surface will push back
against any curvature in much the same way as a ball pushed uphill will push back to
minimize its gravitational potential energy.

An equivalent definition, one that is useful in thermodynamics, is work done per unit
area. As such, in order to increase the surface area of a mass of liquid by an amount,
A, a quantity of work, A, is needed. This work is stored as potential energy.
Consequently surface tension can be also measured in SI system as joules per square
meter and in the cgs system as ergs per cm2. Since mechanical systems try to find a
state of minimum potential energy, a free droplet of liquid naturally assumes a
spherical shape, which has the minimum surface area for a given volume. The
equivalence of measurement of energy per unit area to force per unit length can be
proven by dimensional analysis.

Surface tension forces acting on a tiny differential patch of surface indicate the
amount of bend over the dimensions of the patch. Balancing the tension forces with
pressure leads to the YoungLaplace equation, if no force acts normal to a tensioned
surface, the surface must remain flat. But if the pressure on one side of the surface
differs from pressure on the other side, the pressure difference times surface area
results in a normal force. In order for the surface tension forces to cancel the force
due to pressure, the surface must be curved. The diagram shows how surface
curvature of a tiny patch of surface leads to a net component of surface tension forces

11

acting normal to the center of the patch. When all the forces are balanced, the
resulting equation is known as the YoungLaplace equation:
x y
1 1
p
R R
| |
A = +
|
|
\ .
(2.1)

Equation Section 1Where p is the pressure difference, is surface tension, Rx and
Ry are radii of curvature in each of the axes that are parallel to the surface.
The quantity in parentheses on the right hand side is in fact (twice) the mean
curvature of the surface (depending on normalization).

The thickness of a puddle of liquid on a surface whose contact angle is 180 is given
by
h 2
g
(2.1)
Where h is the depth of the puddle in centimeters or meters, is the surface tension
of the liquid in dynes per centimeter or newtons per meter, g is the acceleration due
to gravity and is equal to 980 cm/s2 or 9.8 m/s2, is the density of the liquid in
grams per cubic centimeter or kilograms per cubic meter.

2.5 Capillary Pressure
In porous media, capillary pressure is the force necessary to squeeze a hydrocarbon
droplet through a pore throat i.e. works against the interfacial tension between oil and
water phases and is higher for smaller pore diameter. When a dry porous medium,
such as a paper or a wick, is brought into contact with a liquid, it will start absorbing
the liquid at a rate which decreases over time. For porous material with cross-

12

sectional area A that is wetted on one end, the cumulative volume V of absorbed
liquid after a time t is
V A S t =
(2.2)

Where S is the sorptivity of the medium with dimension m/s1/2. In physics, the
YoungLaplace equation is a nonlinear partial differential equation that describes the
capillary pressure difference sustained across the interface between two static fluids,
such as water and air, due to the phenomenon of surface tension or wall tension,
although usage on the latter is only applicable if assuming that the wall is very thin.
The YoungLaplace equation relates the pressure difference to the shape of the
surface or wall and it is fundamentally important in the study of static capillary
surfaces. It is a statement of normal stress balance for static fluids meeting at an
interface, where the interface is treated as a surface (zero thickness)
x y
1 1
p
R R
| |
A = +
|
|
\ .
(2.3)

Where p is the pressure difference across the fluid interface, is the surface tension
(or wall tension), and Rx and Ry are the principal radii of curvature. Many refer
inappropriately to the factor 2R as the total curvature. Note that only normal stress is
considered, this is because it can be shown that a static interface is possible only in
the absence of tangential stress.

13

2.6 Viscosity
Viscosity is a measure of the resistance of a fluid which is being deformed by either
shear or tensile stress. In everyday terms (and for fluids only), viscosity is
"thickness" or "internal friction". Thus, water is "thin", having a lower viscosity,
while honey is "thick", having a higher viscosity. Put simply, the less viscous the
fluid is, the greater its ease of movement (fluidity).

The study of flowing matter is known as rheology, which includes viscosity and
related concepts. In general, in any flow, layers move at different velocities and the
fluid's viscosity arises from the shear stress between the layers that ultimately oppose
any applied force. The relationship between the shear stress and the velocity gradient
can be obtained by considering two plates closely spaced at a distance y, and
separated by a homogeneous substance. Assuming that the plates are very large, with
a large area A, such that edge effects may be ignored, and that the lower plate is
fixed, let a force F be applied to the upper plate. If this force causes the substance
between the plates to undergo shear flow with a velocity gradient u/y (as opposed to
just shearing elastically until the shear stress in the substance balances the applied
force), the substance is called a fluid. The applied force is proportional to the area
and velocity gradient in the fluid,
u
F A
y
=
(2.4)

Where is the proportionality factor and it is called the dynamic viscosity. This
equation can be expressed in terms of shear stress = F/A. Thus as expressed in
differential form by Isaac Newton for straight, parallel and uniform flow, the shear

14

stress between layers is proportional to the velocity gradient in the direction
perpendicular to the layers,
u
y
c
t =
c
(2.5)

Hence, through this method, the relation between the shear stress and the velocity
gradient can be obtained. James Clerk Maxwell called viscosity fugitive elasticity
because of the analogy that elastic deformation opposes shear stress in solids, while
in viscous fluids, shear stress is opposed by rate of deformation. General unit
conversions for viscosity are:
1 P = 0.1 Pas,
1 cP = 1 mPas = 0.001 Pas.

2.7 Contact Angle
The contact angle is the angle, conventionally measured through the liquid, at which
a liquid/vapor interface meets a solid surface. The equilibrium contact angle is
specific for any given system and is determined by the molecular interactions across
the liquid/vapor, solid/vapor, and solid/liquid interfaces. A single system of
drop/medium (say air)/surface has a spectrum of contact angles ranging from the so-
called advancing (maximal) contact angle to the receding (minimal) contact angle.
The equilibrium contact angle is between those values and can be estimated from
them as described below. Most often the concept is illustrated with a small liquid
droplet resting on a flat horizontal solid surface. The shape of the droplet is
determined by the Young-Laplace equation, with the contact angle playing the role
of a boundary condition. Contact angle is measured using a contact angle

15

goniometer. The contact angle is not limited to a liquid/vapor interface; it is equally
applicable to the interface of two liquids.

If the molecules of a liquid are strongly attracted to the molecules of a solid (for
example water on a strongly hydrophilic solid) then a drop of the liquid will
completely spread out on the solid surface, corresponding to a contact angle of 0.
Weaker attractions between liquid and solid molecules will result in higher contact
angles. On many highly hydrophilic surfaces, water droplets will exhibit contact
angles of 0 to 30. If the solid surface is hydrophobic, the water contact angle will
be larger than 90. Highly hydrophobic surfaces made of low surface energy (e.g.
fluorinated) materials may have water contact angles as high as ~120. Some
materials with highly rough surfaces may have a water contact angle even greater
than 150, due to the presence of air pockets under the liquid drop. These are called
superhydrophobic surfaces. Sometimes the contact angle is measured through the gas
instead of through the liquid, which would replace all of the mentioned angles by
180 minus their given value.

16

2.8 Porosity, Permeability and Drag Coefficient
Porosity or void fraction is a measure of the void spaces in a material, and is a
fraction of the volume of voids over the total volume, between 01, or as a
percentage between 0100percent. It is defined by the ratio,
V
T
V
V
| =
(2.6)

Where VV is the volume of void-space (such as fluids) and VT is the total or bulk
volume of material, including the solid and void components. Both the mathematical
symbols and are used to denote porosity. Porosity is a fraction between 0 and 1,
typically ranging from less than 0.01 for solid granite to more than 0.5 for peat and
clay. It may also be represented in percent terms by multiplying the fraction by 100.
A value for porosity can alternatively be calculated from the bulk density bulk and
particle density particle,
bulk
particle
1

| =
(2.7)
Paper is Nano-porous materials which consist of a regular organic or inorganic
framework supporting a regular, porous structure. Pores are by definition roughly in
the nanometer range that is between 1x107 and 0.2x109 m.

Permeability in fluid mechanics commonly symbolized as , or k is a measure of the
ability of a porous material to allow fluids to pass through it. Permeability is part of
the proportionality constant in Darcy's law which relates discharge (flow rate) and
fluid physical properties (e.g. viscosity), to a pressure gradient applied to the porous
media,

17

P
x
k A
v =
A
(2.8)

Therefore,
x
P
A
k = v
A
(2.9)
Where is the superficial fluid flow velocity through the medium (i.e., the average
velocity calculated as if the fluid were the only phase present in the porous medium)
(m/s), k is the permeability of a medium (m2), is the dynamic viscosity of the fluid
(Pas), Pis the applied pressure difference (Pa), x is the thickness of the bed of the
porous medium (m).

In fluid dynamics, the drag coefficient commonly denoted as: cd, cx or cw is a
dimensionless quantity that is used to quantify the drag or resistance of an object in a
fluid environment such as air or water. It is used in the drag equation, where a lower
drag coefficient indicates the object will have less aerodynamic or hydrodynamic
drag. The drag coefficient is always associated with a particular surface area. The
drag coefficient of any object comprises the effects of the two basic contributors to
fluid dynamic drag: skin friction and form drag. The drag coefficient of complete
interactions such as a fluid flow also includes the effects of interference drag. The
drag equation,
2
d d
1
F c A
2
= v
(2.10)

18

Cd is not a constant but varies as a function of speed, flow direction, object position,
object size, fluid density and fluid viscosity. Speed, kinematic viscosity and a
characteristic length scale of the object are incorporated into a dimensionless
quantity called the Reynolds number . Cd is thus a function of reynolds number. In
compressible flow, the speed of sound is relevant and Cd is also a function of Mach
number (Ma). The boundary layer will transition from laminar to turbulent providing
the Reynolds number of the flow around the body is high enough. Larger velocities,
larger objects, and lower viscosities contribute to larger Reynolds numbers. At a low
Reynolds number, the flow around the object does not transition to turbulent but
remains laminar, even up to the point at which it separates from the surface of the
object. At very low Reynolds numbers, without flow separation, the drag force Fd is
proportional to v instead of v2; for a sphere this is known as Stokes law. Reynolds
number will be low for small objects, low velocities, and high viscosity fluids.

A Cd equal to 1 would be obtained in a case where all of the fluid approaching the
object is brought to rest, building up stagnation pressure over the whole front surface.

2.9 Navier Stokes Equation
In physics, the NavierStokes equations, named after Claude-Louis Navier and
George Gabriel Stokes, describe the motion of fluid substances. These equations
arise from applying Newton's second law to fluid motion, together with the
assumption that the fluid stress is the sum of a diffusing viscous term (proportional to
the gradient of velocity), plus a pressure term.

19

The derivation of the NavierStokes equations begins with an application of
Newton's second law: conservation of momentum (often alongside mass and energy
conservation) being written for an arbitrary portion of the fluid. In an inertial frame
of reference, the general form of the equations of fluid motion is.
v
v v p T f
t
c | |
+ V = V +V +
|
c
\ .
(2.11)

where v is the flow velocity, is the fluid density, p is the pressure, T is the
(deviatoric) stress tensor, and f represents body forces (per unit volume) acting on
the fluid and is the del operator. This is a statement of the conservation of
momentum in a fluid and it is an application of Newton's second law to a continuum;
in fact this equation is applicable to any non-relativistic continuum and is known as
the Cauchy momentum equation. This equation is often written using the material
derivative Dv/Dt, making it more apparent that this is a statement of Newton's
second law,
Dv
p T f
Dt
= V +V +
(2.12)
The left side of the equation describes acceleration, and may be composed of time
dependent or convective effects (also the effects of non-inertial coordinates if
present). The right side of the equation is in effect a summation of body forces (such
as gravity) and divergence of stress (pressure and shear stress).
The vector field f represents body forces. Typically these consist of only gravity
forces, but may include other types of forces. In a non-inertial coordinate system,
other "forces" such as that associated with rotating coordinates may be inserted.

20

A simplification of the resulting flow equations is obtained when considering an
incompressible flow of a Newtonian fluid. The assumption of incompressibility rules
out the possibility of sound or shock waves to occur; so this simplification is invalid
if these phenomena are important. The incompressible flow assumption typically
holds well even when dealing with a "compressible" fluid such as air at room
temperature at low Mach numbers (even when flowing up to about Mach 0.3).
Taking the incompressible flow assumption into account and assuming constant
viscosity, the NavierStokes equations will read, in vector form.
{ } ( ) f
f f
1 1 1
p A
t V V
o
+ V = V + V +
o
f
u
A u u u G u K
(2.13)

Note that only the convective terms are nonlinear for incompressible Newtonian
flow. The convective acceleration is an acceleration caused by a (possibly steady)
change in velocity over position, for example the speeding up of fluid entering a
converging nozzle. Though individual fluid particles are being accelerated and thus
are under unsteady motion, the flow field (a velocity distribution) will not necessarily
be time dependent.

21

2.10 Colloidal Particles
Colloids form heterogeneous mixtures that are large enough to scatter light. Colloids
usually consist of two phases, or one continuous phase in which the other phase is
dispersed. These particles are larger than the size of molecules, but small enough for
the dispersed phase to stay suspended for a long period of time.

Colloidal systems contain at least one or more substances that have at least one
dimension in the range between 10-9 m (10 A) and 10-6 m (1 m) in size. On the
smaller end of this scale, there are no distinct boundaries between the phases, and the
system is considered a solution. On the larger end of this scale, particles will begin to
fall to the bottom due to gravitational force, and the phases are separated.
Aggregation involves the association of particles to form clusters, and depends on
two distinct influences:

(1) Particles must move in a way that collisions occur, and
(2) Particles that repel each other are said to be stable, since they do not form
aggregates.
Colloids interact with each other at an extremely short range, (usually much less than
than the particle size), so that particles have to approach very close to each other
before any significant interaction is felt. The interaction may be attractive (van der
Waals) or repulsive (electrostatic repulsion, steric). There are many important
properties of colloidal systems that are determined directly or indirectly by the
interaction forces between particles. These colloidal forces consist of the electrical
double layer, van der Waals, Born, hydration, and steric forces. Colloidal particles

22

are dominated by surface properties. If the surface area to volume or surface area to
mass of a spherical particle is looked at, the dependence on the particle radius is
SA/V. This relationship shows that as particles decrease in size, the surface properties
of the particle become increasingly important. The measurement of particle size is
also a defining property. Optical microscopy relies on visible light, which renders
colloidal particles largely invisible to optical techniques. (Visible light limits
measurements to about 0.5 m). Sedimentation cannot be used to characterize
particles because the particles need to be about 1.5 m in size.

2.11 Surface Charge
Colloidal suspensions usually consist of charged particles dispersed throughout a
continuous solvent phase. When two phases are in contact, a separation of charge
will occur which causes a difference in electrical potential. If this phase separation is
restricted to a solid interface with an aqueous electrolyte system, there are several
possible mechanisms for the separation of charge:

1) A difference in affinity of ions for the two phases
2) Ionization of surface groups
3) Physical restriction of certain ions to one phase.

The first case of separation of charge is usually found in metal halides, calcium
carbonate, and metal oxides. The best-known example is silver iodide. When silver
iodide is in contact with pure water, silver ions have a tendency to escape from the 8

23

crystal lattice, leaving a crystal with an excess negative charge. If the concentration
of silver ions is increased, a point is reached where the higher escaping tendency of
the silver ions is balanced by their higher concentration in solution, and the solid
does not have a net charge. For these cases, the surface potential can be modeled by
the Nerst equation:

o i
i
RT
cons tan t lna
Z F
| |
= +
|
\ .
(2.6)

Where R is the gas constant, T is the absolute temperature, F is the Faraday constant,
Zi is the valence, and ai is the activity of the escaping ions.

An example of pH-dependent surface charge is the case of metal oxides. When metal
oxides are in contact with water, the oxide surfaces become hydroxylated, giving the
possibility of surface ionization to yield either positive or negative groups. The
ionization of such groups can be written as:
NaCl Na Cl
+
+ (2.7)
This process involves the loss of charge, which are defined by appropriate
equilibrium constants. The degree of protonation depends on the values of these
equilibrium constants and the solution properties.

2.12 Gouy Chapman Model
If the colloidal particles in solution are charged, and the solution is electrically
neutral, the balancing charge is accounted for by an excess number of oppositely
charged ions or counter ions in solution adjacent to the charged surface and a deficit
of similarly charged ions. In this electrical double layer, the counter ions are

24

distributed according to a balance between their thermal motion and the forces of
electrical attraction. The Gouy-Chapman model characterizes this arrangement of
charged species around the colloidal particle. The electronic double layer is
composed of two layers, the inner layer (Stern layer), and the outer layer (diffuse
layer). The Stern layer consists mainly of oppositely charged ions adsorbed to the
colloid surface. The diffuse layer consists of a mixture of ions extending some
distance away from the colloid. The Shear surface is the surface between the fixed
and diffuse layer and defining the mobile portion of the colloid. A diagram of the
electric double layer is shown in Figures 2.4 and 2.5.

The Gouy and Chapman model is based on a number of simplifying assumptions:

1) An infinite, flat impenetrable interface
2) Ions in solution are point charges, able to approach right up to the interface.
3) The surface charge and potential are uniformly smeared out over the surface.
4) The solvent is a uniform medium with properties (especially permittivity) that are
independent of distance from the surface.

25

Figure 2-3 The Gouy - Chapman Model

Figure 2-4 Potential Profile for Gouy-Chapman Model

The relationship between charge density (cm
-3
) and potential, , at any point is the
Poisson equation:

26

2

V =
c
(2.8)

where is the permittivity of the medium. The Boltzmann Distribution gives the
distribution of positive and negative ions away from the particle surface:

0
ze
n n exp
kT
+
| | |
=
|
\ .
(2.9)

0
ze
n n exp
kT
| | |
=
|
\ .
(2.10)

Where n+ and n- are the number of cations and anions per unit volume with charge
+e and e respectively. N
0
is the number of anions or cations far from the surface
where the average electrostatic potential is zero. T is the absolute temperature and
k the Boltzmann constant, and z is the valence of electrons.

Since a flat interface is being considered, the Poisson-Boltzmann expression will be
used:

2
0
2
2zen d ze
dx kT
| | | |
=
|
c
\ .
(2.11)

The dimensionless parameters are: y = ze/kT and X = kx, where k -z
electrolytes, by:

2 2
2 0
2e n z
k
kT
=
c
(2.12)

27

The Debye-Huckel parameter, k, has the dimensions of reciprocal length and plays a
very important part in the electrical interaction between colloidal particles. The
Gouy-Chapman theory has several short-comings. For example, measured
capacitances at certain interfaces can be much lower than predicted by theory. Also,
counterions concentrations close to charged interfaces can become unreasonably
high, even for moderate values of surface potential.

2.13 Electrophoretic Mobility and Zeta Potential
For a flat surface in a monovalent electrolyte, the electrostatic potential at a distance
x from the surface is related to the surface potential 0 via:

0
4
(x) arctan(h[exp( kx) tanh( e / 4)])
e
= |
|
(2.13)

as follows from the integration of the Poisson-Boltzmann equation. The zeta
potential was computed as the electrostatic potential , = (xs) at some distance xs
from the surface, corresponding to the thickness of an immobile fluid layer, adjacent
to the particle surface. The outer end of this immobile layer, where the motion of
fluid relative to the particle sets in, is commonly referred to as the surface of shear.

2.14 Aggregation
Three of the most basic properties of a particulate system are the particle
composition, particle size distribution, and particle shape. As particles undergo
aggregation, the particle size distribution and shape of the particle can change
dramaticallydepending on the fractal nature of the aggregate structure. The
foundations of the rate of aggregation start from the classic work of Smoluchowski.

28

It is convenient to think in terms of a dispersion of initially identical particles, which,
after a period of aggregation, contains aggregates of various sizes and different
concentrations. A fundamental assumption is that aggregation is a second-order rate
process, in which the collision is proportional to the product of concentrations of two
colliding species. Three-body collisions are usually ignored in treatments of
aggregationthey usually become important at very high particle concentrations.
The number of collisions occurring between i and j particles in unit time and unit
volume, Jij, is given by:

i, j i, j i j
J k n n = (2.14)

where ki,j is a second rate order constant, which depends on a number of factors, such
as particle size and transport mechanism.

In considering the rate of aggregation, it must be recognized that not all collisions
may be successful in producing aggregates. The fraction of successful collisions is
called the collision efficiency and is given the symbol . If there is strong repulsion
between particles, there will not be any collisions that give aggregates and
When there is no significant net repulsion or attraction between particles, then the
collision efficiency can approach unity.

It is normal to assume in aggregation modeling that the collision rate is independent
of colloid interactions and depends only on particle transport. This assumption can be
justified on the basis of the short-range nature of interparticle forces, which operate
over a range which is usually much less than the particle size, so that the particles are

29

nearly in contact before these forces come into play. For the present, it shall be
assumed that every collision is effective in forming an aggregate (collision
efficiency, =1), so that the aggregation rate constant is the same as the collision
rate constant. The rate of change of concentration of k-fold aggregates, where k = i +
j:

i k 1
k
ij i j k ik i
i j k k 1
i 1
dn 1
k n n n k n
dt 2
=
+ =
=
=

(2.15)

The first term on the right-hand side represents the rate of formation of k aggregates
by collision of any pair of aggregates, i and j, such that i + j = k. Carrying out the
summation by this method would mean counting each collision twice and hence the
factor is included. The second term accounts for the loss of k aggregates by collision,
and aggregation, with any other aggregates. The terms kij and kik are the appropriate
rate constants. The above equation is for irreversible aggregation.

2.15 Model Collision Rates
The determination of rate constants for aggregation events is dependent on two
factors:

(1) The mechanism by which particle collisions occur, and
(2) The presence of interparticle interactions.

In considering the nature of particle transport, and correspondingly particle collision,
there are three major mechanisms

30

(1) Brownian motion (Perikinetic aggregation),
(2) Fluid motion (Orthokinetic aggregation), and
(3) Differential sedimentation.

These mechanisms will be discussed in the next few sections. In all cases it is
assumed that particles are spherical and that the collision efficiency is unity.
Hydrodynamic interaction will be neglected in the next few sections.

2.16 Perikinetic Collision Mechanism
Small particles in suspension can be seen to undergo continuous random movements
called Brownian motion. This phenomenon occurs primarily in particles 100 nm to
1000 nm. Brownian motion is temperature dependent, and becomes increasingly
important when particles are one micron or smaller. It is also important under
conditions of high particle concentration (greater than 10 g/L), and low or no shear.
The motion of perikinetic aggregation is shown in

Figure 2-5 Perikinetic Collision Mechanism
Smoluchowski derived an expression for collision frequency in this case by
considering the diffusive flux of the particles towards a stationary particle. Using

31

Ficks law for the number of particles J going through a unit area toward a reference
particle per unit time:

dN
J ' D
dr
= (2.16)

where D is the diffusion coefficient of particles, N is the number concentration, and
r is the radial distance from the center of the reference particle. Smoluchowski
defined a spherical surface around a reference so that any other particle whose center
passes through that boundary will be considered to collide effectively and produce
coagulation.

The number of particles going through a sphere of radius r in unit time is:

2
dN
J ' (4 r )D
dr
= t (2.17)
The diffusion coefficient of a spherical particle is given by the Stokes-Einstein
equation:

i
i
kT
D
6 a
=
t
(2.18)

where k is the Boltzmanns constant, T is the absolute temperature, ai the particle
radius, and the viscosity of the suspending fluid .Smoluchowski calculated the rate
of diffusion of spherical particles of type i to a fixed sphere j:

i ij i i
J 4 R D n = t (2.19)

32

Where Di is the diffusion coefficient of particles of type i and ni is their concentration
in the bulk expression. This collision radius can be considered the center-to-center
distance at which a contact takes place. This is simply the sum of the particle radii:
Rij =ai + aj.

In reality, the central sphere j is not fixed, but is itself subject to Brownian diffusion.
If the concentration of j particles is nj, then the number of i-j collisions occurring in
the unit volume per unit time is:

i ij i i j
J 4 R D n n = t (2.20)

The rate constant for aggregation is now:

( )
2
i j
i, j
i j
a a
2 T
3 a a
+
=
k
k (2.21)
This equation gives the rate constant for perikinetic collisions. For particles of
approximately equal size, the collision rate constant becomes almost independent of
particle size.

2.17 Orthokinetic Collision and Differential Settling Mechanism
Collisions brought about by Brownian motion do not usually lead to the rapid
formation of large aggregates. Particle transport brought about by fluid motion can
give an enormous increase in the rate of interparticle collisions, and aggregation
brought about in this way is known as orthokinetic collision. This type of collision
becomes relevant between 1 and 10 microns. Smoluchowski also was the first to
study the rate of orthokinetic aggregation due to uniform laminar shear forces. A

33

uniform laminar shear field is one in which the fluid velocity varies linearly in only
one direction, perpendicular to the direction of flow. Smoluchowski assumed that
particles would flow in straight lines and collide with particles moving on different
streamlines according to their relative position. The collision frequency depends on
the sizes of the particles and on the velocity gradient or shear rate G. By considering
a fixed central sphere of radius aj and flowing particles of radius ai, it can be assumed
that those moving particles on streamlines that bring their centers within a distance
(ai + aj). The collision frequency can then be calculated by considering the flux of
particles through a cylinder of radius Rij, the axis which passes through the fixed
sphere j. The total flux towards the center particle, Ji is just twice that in one half of
the cylinder and is given by:

ij
R
2 2 3
i i ij i ij
0
J 4Gn z (R z )dz 4Gn R = =
}
(2.22)

Figure 2-6 Orthokinetic Collision Mechanism

34

This equation shows that the rate is proportional to the cube of the collision radius,
which has a major effect on aggregate growth rate. As aggregation proceeds and
aggregate size increases, the chance of capture becomes greater. Another important
collision mechanism arises whenever particles of different sizes and density are
settling from a suspension. Particles of different diameters settle at different
velocities causing the faster moving particles to collide with slower moving particles
leading to aggregation. This type of collision mechanism usually becomes relevant at
particles of 10-100 microns in size and larger. By balancing the forces of gravity,
buoyancy and drag, the sedimentation velocity of a particle of radius ai and density s
in a medium of density is given by Stokes equation:

3
ij s i j i j
2 g
K ( )(a a ) (a a )
9
| | t
= + +
|
\ .
(2.23)

where g is the acceleration due to gravity, s is the density of the particles and is
the density of the fluid.

2.18 Comparison of Rates
A summary of the collision mechanisms described in the previous sections are
summarized below:

Perikinetic
( )
2
i j
i, j
i j
a a
2 T
3 a a
+
=
k
k

35

Orthokinetic
3
ij i j
4
k G(a a )
3
= +
Differential settling
3
ij s i j i j
2 g
K ( )(a a ) (a a )
9
| | t
= + +
|
\ .

Usually it is assumed that the three mechanisms of interparticle collisions are
independent and when they operate simultaneously the aggregation rates are
additive:

total brownian sedimentation shear
J J J J = + + (2.24)

The relative magnitudes of each contribution depend on the characteristics of
suspension and flow conditions. If the densities of the particles and the dispersing
medium are nearly the same, contribution due to sedimentation can be neglected.
Other factors that limit the effect of sedimentation are high viscosity of the
dispersing medium and the relatively small size of particles.

For a comparison of rates, it is convenient to take one particle of fixed size and
compute the various rate constants as a function of the size of the second particle. To
compare the collision frequencies due to shear flow that with due to Brownian
motion, their ratio is characterized by the Peclet number. If Pe >> 1, shear flow
dominates, but if Pe<< 1, Brownian motion will dominate.

3
B
4 a
Pe
k T
q
= (2.25)

36

2.19 Stability Ratio for Perikinetic Collision
The effect of repulsive colloidal interactions on perikinetic aggregation is to give a
reduction in rate. In this approach, a stability ratio, W, is used and is expressed as W
= 1 /o (the reciprocal of the collision efficiency). The stability ratio is simply the
ratio of the aggregation rate in the absence of colloidal interactions. For cases where
only van der Waals attraction and electrical repulsion need to be considered, there is
an energy barrier when the particles approach the particles. The stability ratio can be
calculated by treating the problem as one of diffusion in a force field:
( )
i j
T
i j
2
(a a )
V (l)
exp
kT
W a a dl
l
+
| |
|
\ .
= +
}
(2.26)

where V(l) is the total interaction energy between particles. To evaluate W, the
integral in the last equation has to be evaluated numerically, using appropriate
expressions for the electrical and van der Waals interactions. Due to the exponential
term, most of the contribution to the integral comes from a region close to the
maximum.

2.20 Interparticle Forces
In colloidal systems, there are three basic types of intermolecular forces acting
between molecules:

(1) Van der Waals forces,
(2) Electrostatic forces, and

37

(3) Steric hindrance.

The combinations of these forces control the type and rate of coagulation in
particulate systems. Figure 2-9 shows the potential energy curve for colloidal
interaction.

Figure 2-7 Interaction energy of colloidal particle

2.21 Electrostatic Repulsive Force
The Gouy-Chapman model explains that colloidal particles are surrounded by an
electric double layer, where ions are distributed such that the average electrostatic
potential is represented by Poisson-Boltzmann equation (PBE). When two particles
approach each other, there is interference between the electrostatic double layers
which will result in an increase in energy for the two particles.

A general formula for the force per unit area between two flat approaching double
layer in a symmetrical (z-z) electrolyte was given by Langmuir (1938) and Bell and
Peterson (1972):

38

2
R
d
f n kT 2cosh 2
dx
(
| | |
= |
(
|
k
\ .
(

(2.27)
where n is the bulk number density of ions, u =zev/kT , and 0 denotes the potential
at a distance x from the plate. Integrating the force over distance then gives the
potential energy per unit area uR:

2.22 Van der Waals
Van der Waals forces are present between all colloidal particles. Many physical
phenomena are consequence of these forces. Examples include: the behavior of real
gases, surface tension of liquids, and adsorption of gases on solids and aggregation of
colloidal particles. These forces arise from spontaneous electrical and magnetic
polarizations, giving a fluctuating electromagnetic field within the media and in the
gap between them. Van der Waals forces have several components that correspond to
different molecular interactions, but the most relevant are:

1) Debye or Induction interaction which results from the attraction of permanent and
induced dipoles.
2) Keesom or dipole orientation that acts between permanent dipoles.
3) London or dispersion energy between induced dipoles.

There are two approaches to deriving van der Waals forces:

(1) The classical (microscopic) approach, and
(2) The macroscopic approach.

39

The classical approach is due to Hamaker (1937), the interaction between 2
macroscopic bodies is obtained by the summation of all the relevant intermolecular
interactions.

The Hamaker expressions are based the assumption of pairwise additive of
intermolecular forces. The interaction between two particles is calculated by
summing the interactions of all molecules in one particle with all of the molecules in
the other. Each van der Waals expression can be split into a geometrical part and a
constant A, the Hamaker constant, which is related only to the properties of the
interacting macroscopic bodies and the medium. A is usually in the range of 10-21 J to
10-19 J. Assuming that two equal spheres of radius a1 are immersed in a vacuum, the
result is given by:

A 11 1
V A a / 12h = (2.28)

These expressions apply at close approach, and become quite inaccurate at
separations greater than 10% of the particle radius. In many cases the interaction
energy is negligible at larger distance so that equations like the one above are
acceptable for practical purposes. For interaction of media through a liquid the same
expressions can be used, but with a modified Hamaker constant. A useful
approximation for Hamaker constants of different media is the geometrical mean
assumption:

1/ 2
12 11 22
A (A A ) = (2.29)

40

2.22.1 Other interparticle forces
There are situations where two principle forces alone (double layer and van der
Waals interactions) do not give satisfactory agreement with experimental results. For
colloidal particles carrying adsorbed polymers, the forces are steric or osmotic
forces.

The presence of an adsorbed layer can sometimes have a significant influence on the
stability of colloidal dispersions through one or more of the following mechanisms:

(1) By changing the electrical double layer force either directly, in the case of
polyelectrolytes or by causing a displacement of the Stern surface
(2) By altering the interparticle van der Waals attraction by modifying the effective
Hamaker constant
(3) By generating additional interactions either due to desorption of adsorbed
molecules, or compression and interpenetration of adsorbed layers.

Adsorbed layers can play a very important role in aggregation phenomena. In the
case of colloidal particulate dispersions with larger adsorbed amounts, polymers can
give great stability, by an effect known as steric stabilization. The stabilizing action
of such materials can be interpreted in simple terms. As particles approach
sufficiently close, the adsorbed layers come into contact and any closer approach
would involve some interpretation of the hydrophilic chains. Since these chains are
hydrated, overlap of these layers would cause some dehydration and an increase in
free energy and repulsion between particles. For an initial approximation, the

41

repulsion can be assumed to become infinite as soon as the adsorbed layers begin to
overlap, but zero at greater separations.

42

3 FLUIDIC ANALYSIS AND MATHEMATICAL MODELING

3.1 Introduction
Ink media interactions are using different methods namely Computational Fluid
Dynamics and Mathematical Modeling. In this chapter initially we discuss how
various parameters in Flow3D are defined. Later mathematical model is expressed in
equations and some plots are shown.

3.2 Capillary Pressure
Capillary pressure for fluid flowing through a porous medium can be defined by the
equation:

cap 2
2 (d / 2) cos( ) 4 cos( )
P
(d / 2) d
t o u o u
= =
t
(2.38)

Where Pcap is the capillary pressure, d is the average pore diameter, is the surface
tension, is the contact angle in degrees and all other unit are in cgs system.

Drag Coefficient
It is defined by the equation:

2
1
1
| | |
o =
|
| k
\ .
(2.39)

Where is the drag coefficient, is the porosity which is fixed to 0.5 for entire
calculation and is the permeability of the porous media which is set to 10E-11 cm2.

43

Viscosity and Turbulence
The flow of viscous fluid is considered to be Newtonian viscous flow and the
Reynolds number is less than 2100 so it traverses in laminar flow fashion.
A simple equation to describe Newtonian fluid behavior is

du
dy
t =
(2.40)

Where is the shear stress exerted by the fluid (Pa), is the fluid viscosity - a
constant of proportionality (Pas), du/dy is the velocity gradient perpendicular to the
direction of shear, or equivalently the strain rate (s1)

3.3 Interparticle Forces
The two major contributors to the interparticle interactions are van der Waals
attractive forces and electrostatic repulsion interaction energy. The total interaction
energy between the two aggregating particles will be represented by the sum of these
two forces, which can be expressed mathematically as:
T R A V (H) V (H) V (H) = + (2.30)

Where VT is the total interaction energy for the calculation of the stability ratio, VR
is the electrostatic repulsive interaction energy, and VA is the van der Waals
attractive interaction energy. The accuracy of the stability ratios and the
corresponding aggregation rate constants will be determined by the interparticle
forces used for their calculation.

44

3.4 Van der Waals Attractive Potential
This mathematical model will use the Hamaker theory to model the van der Waals
forces. Hamaker obtained the following expressions for the potential energy of
attraction resulting from van der Waals forces for different geometries. Interaction of
plates of equal thickness:

A 2 2 2
H 1 1 2
V (l)
12 l l 2 1 2
(
= +
(
t + +

(2.31)
where H is the Hamaker constant for the material, is the plate thickness, l is the
plate separation, and VA(l) is the attractive potential of different radii. Hamaker
derived the attractive potential energy for equal spheres of radius a1 and a2 and
surface-to-surface distance H is given by:

2
1 2 1 2 1 2
A
2 2 2
1 2 1 2 1 2 1 2 1 2
A 2a a 2a a h 2a h 2a h
V (H) ln
6 h 2a h 2a h h 2a h 2a h 4a a h 2a h 2a h 4a a
+ + ( | |
= + +
| (
+ + + + + + + +
\ .
(2.32)

Where h= (d1+d2)/2 + s is the distance between the particle center, and s is the
separation distance between surfaces as shown in Figure 3-1. The assumption of
complete additivity is a serious deficiency and the resulting expressions always
overestimate the interaction.

Figure 3-1 Two dissimilar spheres

45

Figure 3-2 Potential Energy of interaction between particles of dissimilar radii
The x-axis of the graph shows the particle separation, while the y-axis shows the
radius of one of the particles while the other is held constant at 100 nm. As the
particle mismatch becomes greater, the interaction energy tends to saturate while the
interaction is dominated by the larger particle. Figure 3.2 shows the interaction
energy as a function of particle surface separation.

3.5 Electrostatic Repulsive Potential
In order to calculate the interaction energy between two particles due to the overlap
of their double layers, it is necessary to know the electrostatic potential profile that
develops between the interacting particles. This is accomplished with the Poisson
Boltzmann equation (PBE), which was introduced in Chapter 2. Solution of PBE will

46

yield the electrostatic potential profile between two surfaces for the given boundary
conditions. Adequate integration of the electrostatic potential will provide the
repulsive potential energy between the interacting surfaces. Unfortunately, the PBE
does not have an analytical exact solution for even the simplest system of two plates
with constant surface potentials. Analytical solutions to the Poisson-Boltzmann
equation are only available for certain values of the surface potential and double-
layer thickness.

Fortunately, aggregation processes are conducted within the range where these
analytical values are valid. The interaction energy is calculated in two different ways
in the mathematical model: linearized Poisson-Boltzmann equation, and the non-
linearized Poisson-Boltzmann equation. Figure 3-2 show the potential energy of
repulsion for different particle sizes with the linearized Poisson-Boltzmann equation,
which is described in Section

3.6 Poisson Boltzmann Equation in Linearized form
The linearized Poisson-Boltzmann equation is based on the solution of Hogg, Healy,
and Fuerstenau, and provides a solution for the electrostatic interaction energy
between two dissimilar sphere and unequal surface potentials:

( )
( ) ( )
( )
( )
( ) ( )
2 2
0 1 2 1 2
1 2
R
2 2
1 2 1 2
a a 1 exp H
2
V (H) ln ln 1 exp 2 H
4 a a 1 exp H
( | | c + + k

= + k
( |
|
+ + k
(
\ .
(2.33)

This expression is limited to ka > 5, and values of the surface potentials up to 70 mV
(Fisher, 1988). This form of the electrostatic interaction energy equation will be

47

abbreviated HHF from now on. Figure 3-3 shows the total interaction energy i.e.
addition of van der waals attractive potential and electrostatic repulsion.

Figure 3-3 Interaction Energy using DLVO theory
3.7 Collision Mechanism
The three collision mechanisms that were presented in Chapter 2 are: perikinetic,
orthokinetic, and sedimentation. They are summarized below:
Perikinetic
( )
2
i j
i, j
i j
a a
2 T
3 a a
+
=
k
k
Orthokinetic
3
ij i j
4
k G(a a )
3
= +
Differential settling
3
ij s i j i j
2 g
K ( )(a a ) (a a )
9
| | t
= + +
|
\ .

48

Figures 3-4 through Figures 3-6 shows the general form for the three collision
mechanisms. Figure 3-4 shows the perikinetic rate constant as a function of particle
size. It is apparent that the aggregation rate constant for the perikinetic case varies
proportionally with temperature and inverse proportionally to solvent viscosity.

Figure 3-4 Perikinetic collision for different particle size

49

Figure 3-5 Orthokinetic collision for different particle size

Figure 3-6 Differential Settling for different particle size

50

3.8 Perikinetic Stability Ratio
The integration of the stability ratios for the perikinetic collision mechanism is
computationally difficult in two ways: (1) the limits to which the integration must be
carried out, and (2) the general form of the integrand. The limits of integration cover
the range from particle contact to infinity. Traditional techniques such as the
trapezoidal rule would require many integration steps to cover the entire range of
integration. To decrease the computational time, and still maintain a high degree of
accuracy, Gaussian quadrature is used. Breaking up the range into many subintervals
using a geometric distribution can also increase the computational efficiency. The
function will be integrated as follows:
( )
i j
T
i j
2
(a a )
V (l)
exp
kT
W a a dl
l
+
| |
|
\ .
= +
}
(2.34)

51

Figure 3-7 Stability ratio for perikinetic collision mechanism
rg is the geometric ratio used to increase the size of the intervals progressively. Each
subinterval uses Gaussian quadrature to increase computational accuracy. Figure 3-7
shows a map of the stability ratios calculated using the HHF approximation using
Poisson-Boltzmann equation.

3.9 Aggregation Coefficient
In Chapter 2, the aggregation kernel is defined in terms of the continuous population
balance model for aggregation. The aggregation coefficient, |, is the rate constant for
two particles. The aggregation coefficient is defined as:

52

Figure 3-8 Aggregation coefficient for different particle size

f
i, j
i, j
W
| =
k
(2.35)

i
i 1
b a h L
i 1
a a L
(x)dx (x)dx (x)dx
+

=
= +
} } }
f f f (2.36)

i
j
i g
j 0
L a h r
=
= +

(2.37)
The stability ratio W for colloidal aggregation is calculated using equation 4.42,
where V
T
(l) is the total interaction potential of two particles. The computational time
in evaluating W can be greatly reduced, while still maintaining accuracy, by using an
efficient integration technique such as Gaussian quadrature. In this method, the
integral in Eq. 2.47 is partitioned into integrals over a number of smaller intervals as

53

shown in Eq. 2.48, and the resulting integrations are converted into simple arithmetic
operations as indicated in Eq. 2.48.

3.10 Population Balance Equation
The population balance equation from Chapter 2 is:

d (L)
B(L) D(L)
dt
=
n
(2.38)
Where the birth and death function are:

( ) ( ) ( )
( )
3 3 1 / 3 3 3 1 / 3
L 2
3 3 2 / 3
0
L , L , ( )d
L
B(L)
2 L
( (

=
}
n n |
(2.39)

0
D(L) (L) (L, ) ( )d
=
}
n n | (2.40)
The discretization method is used to complete the mathematical model.

54

3.11 Discretization Pattern
The accuracy of the population balance models are very importance for the modeling
of the aggregation process because they are the basis of the mathematical model. The
methods of discretion used for this mathematical model are more general in
application than other methods such as orthogonal collocation, and rely less on the
significant tuning of the algorithms for the different initial distributions and
aggregation kernels. The discretization method also is relatively easy to use,
therefore, it is an excellent choice for a general mathematical model. Since the
discretization method plays an important role in this mathematical model, a
derivation of the numerical integration with a thorough error analysis is necessary.

Figure 3-9 Particle Concentration as function of discretized particle volume

55

i 1
i
v
2
v
+
= (2.41)

where vi is the volume, and Li is the length of each discretization bin. Each index I
represent a discrete bin of particle concentration, Ni, which is contained within the
range of particle size between vi and vi+1. Figure 3-9 shows the discrete bins to cover
an arbitrary particle size distribution. This type of geometric discretization allows a
relatively small number of discrete bins to cover a large range of particle sizes.
Hounslow derived the following differential equation which relates the change in
particle characterization in each bin, Ni, to the concentrations in surrounding bins and
the aggregation coefficient, |:

One main disadvantage of this type of discretization is that the particle size divisions
are fixed. Due to this limitation, Litster et al. has improved on the method by
proposing an adjustable discretization method:

1 / q i 1
i
v
2
v
+
= (2.42)
where q is an integer greater than or equal to one, known as the adjustable
discretization parameter. The number of discretization bins for a given particle size
domain can be increased by increasing the adjustable parameter. This type of
discretization still covers a wide range of particle sizes with fewer discretizing bins
than linear discretization, and the fineness of discretization can be customized for
comparison with experimental results. A general development of the derivation of
Litster et al. discretization method is presented below. The development starts by

56

defining the basic aggregation events between sets of particles. The event fall into
five categories:
Particles are created within the interval with the following events:
Type 1: Some of the interactions give particles in the ith interval and give some
particles smaller than the ith interval.
Type 2: All interactions give particles in the ith interval.
Type 3: Some interactions give particles in the ith interval and some give interactions
larger than the ith interval. Particles are removed from the interval by the following
events:
Type 4: Some interactions remove particles from the ith interval.
Type 5: All interactions remove particles from the ith interval.

( ) ( ) ( )
( ) ( )
1 1 / 1 1 / 1 / 1 (1) 1 ( )
1, 1 , 1/ 1/
1 1 ( 1)
1 1 / 1 / 1/ 1 1 ( 1)
2
, , 1/
1 ( )
2 2 1 2
+
2 1 2 1
1 2 2 2

2 2
+ +

= = =
+ + +

= +
| | | |
+
=
| |
| |

\ . \ .
+
+ +

i q
j q j q k q S q S k
i
i j i j i k j i k j q q
j k j i S k
j q k q q S k
i q j q i k j i k j
j i S k
dN
N N N N
dt
N N N
| |
| |
( )
1
1
1 / 1 (1) 1
, , 1/
1 1 (1) 2
1
2

2 1
=
+
= = +
| |
|
|
\ .
| |

|
|
\ .

q
q
k
j q S
i j i j i j i j q
j j S
N N N N | |
(2.43)

p/q
qln(1 2 )
S(p) Int 1
ln 2
(
=
(

(2.44)

In this method of discretization, no integration within subintervals is necessary
unlike the methods of Gelbard and Seinfeld (1980) and Landgrebe and Pratsinis
(1990). The implementation of the discretization method presented, results in a setoff
ordinary differential equations, one differential equation per discretization bin. These

57

differential equations can be evaluated with relative ease, and can be implemented on
any personal computer. The current algorithm is implemented with MATLAB
R2007b using a Runge-Kutta- Fehlberg integration routine with error control.

Figure 3-10 Flow chart for mathematical modeling

58

4 RESULTS

4.1 Introduction
This chapter will show the experimental results from the simulation and
mathematical modeling. Time to absorb, depth of penetration and width of absorbed
droplet are the output variable while surface tension, viscosity, porosity, pore
diameter, capillary pressure are varied in different permutation and combination to
study the effect of each factors thus to ensure agreement with current literature on
colloidal aggregation.

4.2 Simulation
The different values used for the ink media absorption study is shown below:
Table 1 various parameters used for the study
Volume
of
droplet
(pl)
Viscosity
(cP)
Surface
Tension
(dyne/cm)
Pore
Diameter
(m)
Contact
Angle
(degree)
Porosity Velocity (cm/s)
3 2 28 3 45 0.5 500
6.5 4 36 5 1250
10 45 2000

59

4.2.1 Example 1
The first set of experimental runs is carried out for 3pl volume droplet and in this
experimental run the values for the different parameters are:
Table 2 Input variables for example 1
Experimental Parameter Values
Volume of droplet (pl) 6.5
Viscosity (cP) 4
Surface Tension (dyne/cm) 45
Pore Diameter (m) 3
Contact Angle (degree) 45
Porosity 0.5
Capillary Pressure (dyne/cm
2
) 4.24E+04

Drag Coefficient (cm
-2
) 1.00E+11

Velocity (cm/s) 2000

Figure 4-1 (a) 6.5pl drop at time = 0 (b) drop hitting the porous surface at 12.5 m/s

60

Figure 4-2 6.5pl droplet after steady state

Table 3 Output values for example 1
Output Parameter Values
Time (ms) 17.9
Width (m) 60
Height (m) 6.67

4.2.2 Example 2
In this experimental run is done with same set of variables as done in example 1 but
the volume is changed to 10pl.

61

Volume of droplet (pl) 10
Viscosity (cP) 2
Pore Diameter (m) 5
Porosity 0.5
2
) 1.58E+04

-2
) 1.00E+11

Velocity (cm/s) 1250

Figure 4-3 (a) 10pl drop at velocity 12.5 m/s (b) after hits the surface

62

Figure 4-4 drop after steady state

Time (ms) 15.75
Width (m) 67.7
Height (m) 6.4

4.2.3 Example 3
In this experimental run is done with same set of variables as of example 2 but the
volume is changed to 10pl and velocity of incoming droplet is increased to 20m/s.

63

Volume of droplet (pl) 10
Viscosity (cP) 2
Pore Diameter (m) 5
Porosity 0.5
2
) 1.58E+04

-2
) 1.00E+11

Velocity (cm/s) 500

Figure 4-5 (a) 3pl drop hitting at 5 m/s (b) after hitting the surface

64

Figure 4-6 Drop after steady state
Time (ms) 32.5
Width (m) 61.2
Height (m) 7.5

65

4.2.4 Comparison of results
4.2.5 Time versus Surface Tension plots

Figure 4-7 Time vs. Surface tension for various volume of droplet

Figure 4-8 Time vs. Surface tension for various viscosities

66

Figure 4-9 Time vs. Surface tension for various pore diameter
4.2.6 Width versus Surface Tension plots

Figure 4-10 Width vs. Surface tension for various volume of droplet

67

4.2.7 Height versus Surface Tension plots

Figure 4-11Height vs. Surface tension for various volume of droplet

4.3 Mathematical Model
4.3.1 Example 1
The parameters for these experiments are listed table below:
Smallest particle size (nm) 80
Largest particle size (nm) 400
Diameter of monodisperse particle (nm) 130
Particle number concentration 1.49E9
Zeta potential (mV) 30
Ionic concentration (mol/m
3
) 100
Valency 1

Temperature 298

68

Figure 4-12 Particle Number vs. time for valency = 1
4.3.2 Example 2
The parameters for these experiments are listed Table below
Smallest particle size (nm) 80
Largest particle size (nm) 400
Diameter of monodisperse particle (nm) 130
Particle number concentration 1.49E9
Zeta potential (mV) 30
Ionic concentration (mol/m
3
) 100
Valency 2
Temperature 298

69

Figure 4-13 Particle Number vs Time for valency = 2

70

4.4 Comparison between particle aggregation in NaCl and CaCl
2

Particle Concentration vs time for
valency equal to one
Particle Concentration vs time for
valency equal to two

t = 0s

t = 0s

t = 10s

t = 10s
t = 25s

t = 25s

71

t = 50s

t = 50s

t = 100s

t = 100s

t = 150s

t = 150s

72

t = 200s

t = 200s

t = 250s

t = 250s

73

5 Appendix
5.1 Time, Width and Height
Table 8 various input and output values for 3pl

Viscosity(m) Surface
Tension
(dyne/cm)
Pore
Diameter
(m)
Capillary
Pressure
(dyne/cm
2
)
Velocity
(cm/s)
Time
(ms)
Width
(m)
Height
(m)
2 28 3 2.64E+04 500 11.83 40 6.3
2 28 3 2.64E+04 1250 8 47.34 4.4
2 28 3 2.64E+04 2000 7.9 50 5.33
2 28 5 1.58E+04 500 17 40.66 6
2 28 5 1.58E+04 1250 13.4 47.34 6
2 28 5 1.58E+04 2000 11.6 50 5.33
2 36 3 3.39E+04 500 9.5 40 6.2
2 36 3 3.39E+04 1250 7.25 44.2 5.1
2 36 3 3.39E+04 2000 6.2 50 5.33
2 36 5 2.04E+04 500 14 41.04 6.2
2 36 5 2.04E+04 1250 12.65 44.2 6
2 36 5 2.04E+04 2000 9 50 5.33
2 45 3 4.24E+04 500 7.75 40.2 5.9
2 45 3 4.24E+04 1250 6 44 5.3
2 45 3 4.24E+04 2000 4.9 50 5.33
2 45 5 2.55E+04 500 11.25 41 6.2
2 45 5 2.55E+04 1250 9.55 44 6
2 45 5 2.55E+04 2000 7.7 48 5.33
4 28 3 2.64E+04 500 25.25 39.4 6.33
4 28 3 2.64E+04 1250 23.2 39.34 6
4 28 3 2.64E+04 2000 19 45.33 6
4 28 5 1.58E+04 500 35.75 38.6 5.4
4 28 5 1.58E+04 1250 32.45 44 6
4 28 5 1.58E+04 2000 28.3 44 6
4 36 3 3.39E+04 500 20.5 39.34 6.4
4 36 3 3.39E+04 1250 17.75 40 6.2
4 36 3 3.39E+04 2000 14.8 45.33 6
4 36 5 2.04E+04 500 29.75 38.8 6.3
4 36 5 2.04E+04 1250 35.85 44 6
4 36 5 2.04E+04 2000 21.9 45.33 6
4 45 3 4.24E+04 500 16.5 39.34 6.3
4 45 3 4.24E+04 1250 14.25 41.2 5.9
4 45 3 4.24E+04 2000 17.2 45.33 6
4 45 5 2.55E+04 500 22.35 39.34 6
4 45 5 2.55E+04 1250 21.2 41.2 6
4 45 5 2.55E+04 2000 17.6 45.33 6

74

Table 9 various input and output values for 6.5pl
Viscosity(
m)
Surface
Tension
(dyne/cm)
Pore
Diame
ter
(m)
Capillary
Pressure
(dyne/cm
2
)
Velocit
y
(cm/s)
Time
(ms)
Width
(m)
Heig
ht
(m)
2 28 3 2.64E+04 500 20 54 7.3
4 28 3 2.64E+04 500 40.5 50.8 7.5
2 36 3 3.39E+04 500 14.5 54 7.35
4 36 3 3.39E+04 500 24 58 8
2 45 3 4.24E+04 500 13.75 61.2 8
4 45 3 4.24E+04 500 34.5 56.4 9
2 28 3 2.64E+04 1250 13.7 61.33 6.67
4 28 3 2.64E+04 1250 33.2 56 7.33
2 36 3 3.39E+04 1250 10.9 61.33 6.67
4 36 3 3.39E+04 1250 25 57.33 7.33
2 45 3 4.24E+04 1250 9 60 7.33
4 45 3 4.24E+04 1250 21.5 57.33 7.33
2 28 3 2.64E+04 2000 11.8 65.34 6.67
4 28 3 2.64E+04 2000 26.3 60 6.67
2 36 3 3.39E+04 2000 8.6 68 6
4 36 3 3.39E+04 2000 22.1 60 7.33
2 45 3 4.24E+04 2000 7.45 65.34 6.67
4 45 3 4.24E+04 2000 17.9 60 6.67
2 28 5 1.58E+04 500 27.5 55.2 7
4 28 5 1.58E+04 500 55.65 62.2 6.7
2 36 5 2.04E+04 500 24.35 60 6.7
4 36 5 2.04E+04 500 50.25 49.2 6.7
2 45 5 2.55E+04 500 20.75 61.2 8
4 45 5 2.55E+04 500 49.5 55.6 8
2 28 5 1.58E+04 1250 20.3 61.33 6.67
4 28 5 1.58E+04 1250 49 56 6.67
2 36 5 2.04E+04 1250 15.5 62.33 6.67
4 36 5 2.04E+04 1250 37.7 57.33 6.67
2 45 5 2.55E+04 1250 12.1 62.66 6.67
4 45 5 2.55E+04 1250 32.2 57.33 7.33
2 28 5 1.58E+04 2000 17.6 64.34 6
4 28 5 1.58E+04 2000 41.7 60 6
2 36 5 2.04E+04 2000 13.6 66.66 6
4 36 5 2.04E+04 2000 33 60 6.67
2 45 5 2.55E+04 2000 11.4 65.34 6
4 45 5 2.55E+04 2000 26.1 60 6.67

75

Table 10 various input and output values for 10pl
Viscosity(m) Surface
Tension
(dyne/cm)
Pore
Diameter
(m)
Capillary
Pressure
(dyne/cm
2
)
Velocity
(cm/s)
Time
(ms)
Width
(m)
Height
(m)
2 28 3 2.64E+04 500 21.5 61 7.5
2 36 3 3.39E+04 500 17.25 61.2 7.8
2 45 3 4.24E+04 500 13.75 61.2 8.1
2 28 5 1.58E+04 500 32.5 61.2 7.5
2 36 5 2.04E+04 500 25 61.6 7.9
2 45 5 2.55E+04 500 20 61.6 8
2 28 3 2.64E+04 1250 15.9 68 6.7
2 36 3 3.39E+04 1250 12.75 68.1 6.4
2 45 3 4.24E+04 1250 10.95 66.7 7
2 28 5 1.58E+04 1250 15.75 67.7 6.4
2 36 5 2.04E+04 1250 13.45 68 6.4
2 45 5 2.55E+04 1250 11.95 66.7 7
2 28 3 2.64E+04 2000 13.1 70.3 6
2 36 3 3.39E+04 2000 11.65 67.7 6
2 45 3 4.24E+04 2000 10.3 66.7 5.66
2 28 5 1.58E+04 2000 11.35 71.2 6
2 36 5 2.04E+04 2000 8.95 68.1 6
2 45 5 2.55E+04 2000 8.15 66.7 5.66
4 28 3 2.64E+04 500 21.5 61.2 7.9
4 36 3 3.39E+04 500 30 63.34 7
4 45 3 4.24E+04 500 34.35 56.6 8.9
4 28 5 1.58E+04 500 75.3 53.2 8
4 36 5 2.04E+04 500 57.3 56.2 8
4 45 5 2.55E+04 500 48.5 55.4 8
4 28 3 2.64E+04 1250 39.15 62.3 7.1
4 36 3 3.39E+04 1250 32.1 62.6 7.33
4 45 3 4.24E+04 1250 27.8 61.6 7.4
4 28 5 1.58E+04 1250 45.25 62.3 7
4 36 5 2.04E+04 1250 35.6 61.6 7.33
4 45 5 2.55E+04 1250 29.45 61.6 7.4
4 28 3 2.64E+04 2000 18.65 64.3 5.66
4 36 3 3.39E+04 2000 16.3 61.6 5.66
4 45 3 4.24E+04 2000 14.3 61.6 5.34
4 28 5 1.58E+04 2000 20.7 64.2 5.66
4 36 5 2.04E+04 2000 17.85 61.6 5.34
4 45 5 2.55E+04 2000 15.35 61.3 5.34

76

References

[1] Behrens, S. H., Borkovec, M., & Schurtenberger, P. (1998). Aggregation in
charge-stabilized colloidal suspensions revisited. Langmuir, 14(8), 1951-
1954.

[2] Stoll, S., & Buffle, J. (1998). Computer simulation of flocculation processes:
the roles of chain conformation and chain/colloid concentration ratio in the
aggregate structures. J Colloid Interface Sci, 205(2), 290-304.

[3] Behrens, S. H., Christl, D. I., Emmerzael, R., Schurtenberger, P., &
Borkovec, M. (2000). Charging and aggregation properties of carboxyl latex
particles: Experiments versus DLVO theory. Langmuir, 16(6), 2566-2575.

[4] H.C.Hamaker (1937). The London-Van Der Waals attraction between
spherical particles. Physica, 10(3).

[5] Wilson, B. A., & Crimp, M. J. (1993). Prediction of Composite Colloidal
Suspension Stability based upon the Hoog, Healy, and Fuerstenau
Interpretation. Langmuir, 9(11), 2836-2843

[6] Scott M. Fisher. (1998) A mathematical model for aggregation in colloidal
system. M. Sci. Thesis, Univ. S. Florida.

[7] Behrens, S. H., & Borkovec, M. (1999). Electric double layer interaction of
ionizable surfaces: Charge Regulation for Arbitrary Potentials, J. Chem.
Phys. 111, 382-385.

Analysis of Colloidal Pigment Aggregation and Ink Media Interactions in Porous Medial

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ANALYSIS OF COLLOIDAL PIGMENT

AGGREGATION AND INK MEDIA

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