Thesis for the degree of Licentiate Sundsvall 2011

INK-PAPER INTERACTIONS AND EFFECT ON PRINT QUALITY

IN INKJET PRINTING

Anna Lundberg

Supervisor: Dr. Jonas Örtegren, Mid Sweden University

Examiner: Prof. Hans-Erik Nilsson, Mid Sweden University
Assistant supervisor: Prof. Göran Ström, Innventia

Department of Information, Technology and Media.

Mid Sweden University, SE-851 70 Sundsvall, Sweden

ISSN 1652-8948
Mid Sweden University Licentiate Thesis No. 57
ISBN 978-91-86694-23-4
Akademisk avhandling som med tillstånd av Mittuniversitetet i Sundsvall
framläggs till offentlig granskning för avläggande av teknologie licentiatexamen
fredagen den 25 februari 2011, klockan 10.00 i sal ”Skeppet”, Mittuniversitetet
Örnsköldsvik.
Seminariet kommer att hållas på svenska.

INK-PAPER INTERACTIONS AND EFFECT ON PRINT QUALITY

IN INKJET PRINTING
Anna Lundberg

© Anna Lundberg, 2011

Department of Information, Technology and Media.

Mid Sweden University, SE-851 70 Sundsvall
Sweden

Telephone: +46 (0)771-975 000

Printed by Kopieringen Mid Sweden University, Sundsvall, Sweden, 2011

I
INK-PAPER INTERACTIONS AND EFFECT ON PRINT QUALITY
IN INKJET PRINTING

Anna Lundberg

Department of Information, Technology and Media.

Mid Sweden University, SE-851 70 Sundsvall, Sweden
ISSN 1652-8948, Mid Sweden University Licentiate Thesis No 57; ISBN 978-91-
86694-23-4

ABSTRACT

This thesis concerns paper and ink interactions related to inkjet printing. The
main purpose of this work was to gain a deeper understanding in which
parameters control the flow of ink into papers and how the ink interacts with the
paper surface. The overall objective was to find key parameters to optimize the
print quality in inkjet printing.
Characterization of paper-surfaces in terms of porosity, surface roughness and
surface energy was made. Objective and subjective measurements were used for
print quality evaluation. Light microscopy imaging and SEM was used to see how
ink interacts with the paper surface in a printed image. A high speed camera was
used to study the absorption of picolitre sized inkjet droplets into fine papers.
An initial study on the effect of paper properties on print quality was made.
Result indicated that there were small differences in print quality for pilot papers
with different composition (in a specific parameter window) and the commercial
paper COLORLOK® reproduced a noticeable high colour gamut compared to the
other samples.
Research was made to see how surface fixation can affect the print quality for
printouts made with pigmented ink. Surface fixation promotes retention of the
pigmented colorant in the outermost surface layer of the paper and has been
denoted “colorant fixation” in this thesis.
It was shown that applying colorant fixation onto a paper surface before
printing can increase the detail reproduction in a printed image. Different
concentrations of calcium chloride were applied onto the paper surface on full-
scale produced non-commercial papers. Test printing was made with a SoHo
(Small office/Home office) printer using pigmented ink and results showed that

II
using calcium chloride as surface treatment can lead to aggregation of pigments at
the surface resulting in a higher detail reproduction.
Fast absorption of the carrier liquid into the paper and fast fixation of
colourants on the surface is important in inkjet printing to avoid colour to colour
bleeding. These demands will be more pronounced when the printing speed
increases.
It is important to understand which parameters affect the absorption process to
be able to control the mechanisms and to optimize the print quality.
A study of absorption of picolitre size inkjet droplets into fine paper was made
in this work. Theoretical equations describing fluid absorption into capillaries were
tested and compared with experimental results. The result showed that the time
dependence in the Lucas-Washburn (L-W) equation fits fairly well to data whereas
the L-W equation overestimates the penetration depth.
The results are directly applicable to paper and printing industry and can be
used as a base for future studies of absorption of picolitre sized droplets into
porous materials and for studies of aggregation of colloidal particles on surfaces.

KEYWORDS: inkjet, print quality, printability, ink absorption, Lucas-

Washburn equation, dyes, pigments, colourant

III
SAMMANDRAG

Den här avhandlingen handlar om papper och bläck interaktioner relaterat till
inkjettryck. Syftet var att få en djupare förståelse av hur papprets egenskaper kan
påverka och styra de mekanismer som sker vid inkjettryck samt att förstå hur detta
kan relateras till tryckkvalitet.
Objektiva mätningar av tryckkvalitet har utförts tillsammans med subjektiva
utvärderingar i perceptionsstudier. Ljusmikroskopi och SEM har använts för att se
hur bläck interagerar med pappersytan. En höghastighetskamera har använts för
att utföra studier av absorption av picoliterstora droppar i papper.
En inledande studie av hur tillsatser i papper påverkar tryckkvaliteten för
inkjetutskrifter med SoHo skrivare (Small office/Home office printers) har utförts.
Denna studie utfördes för att få en överblick över området. Resultat från denna
studie visar på små skillnader i tryckkvalitet mellan olika pilotpapper samt att
bland kommersiella prover gav det med COLORLOK® en avsevärd större
färgrymd än de andra kommersiella obestrukna proverna.
Det är känt att ytfixering (fixering av färgämne till ytan) ger en högre
tryckdensitetet för obestrukna papper. I detta arbete har studier gjorts för att se hur
ytfixeringsmedel kan ge en förbättrad detaljåtergivning.
Forskning med kalciumklorid som ytfixeringsmedel har utförts genom att olika
salt-koncentrationer lagts på fullskaligt tillverkade icke-kommersiella papper.
Resultat visar att salt som ytfixeringsmedel kan leda till en aggregering av
färgpigmenten på ytan som kan ge en förbättrad detaljåtergivning och en högre
tryckdensitet.
Vid tryckning med höga hastigheter, s.k. höghastighetsinkjet ställs höga krav
på att bärarvätskan snabbt skall absorberas in i papperet och att färgämnena skall
stanna vid ytan. Det är viktigt att förstå vilka parametrar som påverkar
absorptionsförloppet för att kunna kontrollera detta förlopp. I detta arbete har en
studie av absorption av picoliterstora inkjetdroppar in i papper utförts.
Den teoretiska beskrivningen av absorption av vätska i kapillärer enligt Lucas–
Washburn ekvationen har studerats och jämförts med experimentella data.
Reultatet visar att tidsberoendet i L-W ekvationen stämmer väl överens med
experimentella data, medan L-W ekvationen överskattar penetrationsdjupet vid
absorption av picoliterstora bläck droppar i papper.
Resultaten från denna avhandling är direkt tillämpbar inom både
pappersindustrin och vid utveckling av tryckmetoder och kan ligga till grund både
för fortsatta studier av absorption av picoliterstora droppar i porösa material och
för fortsatta studier av aggregering av kolloidala partiklar på yta.

IV
AKNOWLEDGEMENTS

First of all, I want to thank You for reading my thesis! It makes it worth every
minutes of writing.

This thesis is a result from work made within the “Next generation substrates for
inkjet printing” project in which I have been working together with colleagues
from the institute for surface chemistry (YKI), EKA chemicals, Innventia, MoRe
research, M-real, KODAK and DPC. It has been three intensive years with many
interesting challenges. I want to thank all representatives within the reference
group for their engagement in the project.

I am grateful to all valuable support and help that Kristina Wågberg at M-real has
given. Her enthusiasm and engagement have inspired me a lot during this work.

The pleasant atmosphere of DPC has played an important role in this work. I want
to especially thank all doctoral students and senior researchers at DPC for many
fruitful discussions during this time. I would like thank my supervisor Jonas
Örtegren for his confidence in me and support throughout this work.

I want to thank my assistant supervisor Göran Ström at Innventia, Elisabeth

Alfthan, and my friend Thomas Mejtoft at Umeå University for support and
valuable comments to the manuscripts.

Birgitta Sjögren, Birgitta Lundgren, Carin Nordin and Marie Tjärnström at MoRe
Research and Eva Sjöström and Rodrigo Robinsson at YKI for their help with
laboratory work.

People at M-real, MoRe Research and students at DPC for participating in

perception studies.

Last, but not least, I would like to thank all my friends, my family and especially
Jonny who has always been there for me and who never stopped believing in me.

Thank you all!

V
TABLE OF CONTENTS

ABSTRACT ....................................................................................................................... II

SAMMANDRAG ............................................................................................................ IV

AKNOWLEDGEMENTS ................................................................................................ V
LIST OF PAPERS ......................................................................................................... VIII

1. INTRODUCTION ......................................................................................................1

2. BACKGROUND .....................................................................................................2

2.1. INKJET TECHNOLOGY ..............................................................................................2

2.1.1. Historical overview ........................................................................................3
2.2. INKJET INK ..............................................................................................................5
2.3. INKJET PAPER ..........................................................................................................6
3. THEORY ..................................................................................................................7

3.1. PAPER OPTICS .........................................................................................................7

3.1.1. Light and colour .............................................................................................7
3.1.2. CIE L*a*b* ....................................................................................................9
3.2. WETTING AND SPREADING ....................................................................................10
3.2.1. Contact angle ...............................................................................................10
3.2.2. Surface energy/ Surface tension ...................................................................10
3.3. ABSORPTION .........................................................................................................12
3.3.1. Lucas-Washburn equation............................................................................12
4. METHODS AND MEASUREMENTS ..............................................................14

4.1. COLOR MEAUREMENTS .........................................................................................14

4.2. LINE QUALITY .......................................................................................................14
4.3. PERCEPTION STUDY ...............................................................................................16
4.4. SURFACE CHARACTERISTICS .................................................................................16
4.4.1. Surface tension and Contact angle measurements .......................................16
4.4.2. Porosity ........................................................................................................16
4.4.3. Surface roughness ........................................................................................16
4.4.4. Absorption of picolitre size droplets into papers..........................................17
5. SUMMARY OF THE PAPERS ...........................................................................18

5.1. PAPER I .................................................................................................................18

VI
 5.2. PAPER II................................................................................................................19
5.3. PAPER III...............................................................................................................19
5.4. PAPER IV ..............................................................................................................20
6. CONTRIBUTION TO THE THESIS.................................................................21

6.1. PAPER I .................................................................................................................21

6.2. PAPER II................................................................................................................21
6.3. PAPER III...............................................................................................................22
6.4. PAPER IV ..............................................................................................................22
7. DISCUSSION AND FUTURE WORK .................................................................22

8. CONCLUSIONS .......................................................................................................24

9. REFERENCES........................................................................................................25

VII
LIST OF PAPERS

This thesis is mainly based on the following papers, herein referred to by their
Roman numerals. The papers are appended at the end of the thesis.

Paper I On the Effect of Variations in Paper Composition on Inkjet Print Quality.

Lundberg A, Örtegren J, Alfthan E.
In Proc. 25th international Non Impact Printing conference,
Kentucky, Louisville, pp. 316-319, (2009)

Paper II Improved Print quality by Surface fixation of Pigments

Lundberg A, Wågberg K, Norberg O, Örtegren J.
In Proc. 26th international Non Impact Printing conference, Austin,
Texas, pp. 251-255, (2010)

Paper III Aggregation of Color pigments by Surface fixation treatment.

Lundberg A, Örtegren J, Norberg O.
Manuscript submitted to Journal of Imaging Science and
technology, (2011)

Paper IV Micro scale droplet absorption into paper for inkjet printing.
Lundberg A, Örtegren J, Alfthan E, Ström G,
Accepted for publication in Nordic Pulp and Paper Research
Journal, (2010)

VIII
 1. INTRODUCTION

Inkjet is a widely used printing technology, both for production interest and for
home office printing. The print quality for inkjet is high and digital printing opens
up possibilities for a new market with variable data printing, personalized printing
and print on demand.
Until today the main challenge with digital printing has been the low speed,
resulting in high costs for long production runs. The fast development of new
techniques has lead to high speed printing techniques.
Inkjet printing is a non impact printing method where the droplets are ejected
from a nozzle and projected onto a substrate without any contact between the print
head and the substrate. The droplets are settled on the surface and depending on
the characteristics of the ink and paper the drop starts to spread and partly
penetrate the substrate.
The absorption of ink into the substrate controls the printability of the papers in
terms of ink setting rate (wetting, capillary flow, separation of colourant from
solvent, absorption, diffusion and fixation of colourants). The ink setting rate
strongly depends on the characteristics of the ink and paper and on the printing
method as well.
One of the challenges with high speed printing using inkjet technology is to
find the right combination of substrate and ink. The need to understand which
parameters control the ink setting rate increases when the printing speed increases.
The overall aim with this thesis was to gain a deeper knowledge in inkjet
printing and an increased understanding in which parameters affect the dynamics
and interactions between inkjet ink and papers.
The investigation addresses following work: An introduction to print quality
studies on commercial papers and on uncoated pilot papers with different
composition (Paper1). A print quality study on surface treated papers to see how
colourant fixation can improve detail reproduction in a final image (Paper II) and a
study of aggregation of pigments on salt treated surfaces related to detail
reproduction (Paper III). A study of absorption of picolitre size inkjet droplet
printed onto different paper samples (paper IV).

1
2. BACKGROUND

2.1. Inkjet technology

The two main technologies for inkjet are Drop On Demand (DOD) and
continuous inkjet (CIJ). A map that illustrates an overview of Inkjet technology is
depicted in Figure 1 [1]. A common method for CIJ is the piezoelectric technology.
In a continuous (piezo) inkjet print head a piezoelectric crystal divides an ink
stream into droplets. The droplets pass a charge electrode that charges the droplets
depending on the image. The CIJ process can be divided into two processes: Binary
and multi deflection. In a binary deflection process, the droplets have two states of
charge: uncharged for conveyance to the paper and charged for defection in an
electrical field. In a multi deflection process the drops receive different charges so
that they can be deflected in different directions on the substrate.
Drop On demand (DOD) processes generates a droplet only if the printed
image requires a drop. Classification of drop on demand processes is made based
upon the way the droplets are created. In thermal inkjet the ink is heated up until it
vaporizes and ink is ejected from the nozzle as a result of the pressure from the
vapor bubble in the chamber. In piezo inkjet systems a piezo electric material is
vibrating depending on the applied voltage, resulting in variations in volume in
the chamber that lead to ink drop from the nozzles. There are different types of
electrostatic inkjet process variants [1]. Common for all processes is that an
electrical field exists between the inkjet system and the surface to be printed. A
drop is ejected from the nozzle when a control pulse (electrical signal or supply of
heat) disturb the balancing forces in the system.

Figure 1. Overview of inkjet processes [1]. CIJ processes can be binary

deflection or multi deflection. DOD can use thermal, piezo or
electrostatic technology.

2
2.1.1. Historical overview
Inkjet printing is a non impact printing method where the final print is a result
of deposition of inkjet droplets onto a substrate in a pre-defined pattern. The final
print is strongly affected by both drop formation and interaction between ink and
paper.
The initial studies of drop formation were made by Abbé Nollet in 1749. He
demonstrated how a stream of liquid could be manipulated by static electricity [2-
3].
The first inkjet-like recording device, a “Siphon recorder” was invented by Lord
Kelvin in 1858. This device can be used for recordings of telegraph messages
(Figure 2).
A Siphon device produces a continuous stream of ink onto a moving substrate
and a driving signal moves the Siphon back and forth to create a pattern on the
substrate.

Figure 2. The siphon recorder invented by Lord Kelvin in 1858.

The foundation of modern inkjet technology is attributed to the Belgian
physicist Joseph Plateau and the English physicist Lord Rayleigh.
In 1856 Plateau published ”On the recent theories of the constitution of jet
liquid issuing from circular orifices” [4] and ten years later he derived the
relationship between a droplet size to jet diameter.
In 1878 Lord Rayleigh demonstrated how a stream of liquid could be divided
into droplets [5]. This publication was the first in a series of publications that has
come to be of great importance to modern inkjet technology.
The application of Lord Rayleigh´s research ended up in a”Rayleigh break-up
device” and later on in a production of a “Mingograph”, described in the US patent
released in 1952 [6].
In the early 1960s, Dr. Sweet of Stanford University demonstrated that by
applying a pressure wave pattern to an orifice, the ink stream could be broken into

3
droplets of uniform size and spacing. The droplets could then be charged and
deflected when passing through an electrical field to form an image on the
substrate. The uncharged droplets were captured by a gutter and recirculated into
the system. This version is known as continuous inkjet [7] with the “inkjet
oscillograph” as first device.
Drop on demand (DOD) is another technique for inkjet printing where a drop is
created only when an actual pulse is provided.
The first work in this direction was made in the late 1940s by Hansell of the
Radio Corporation of America (RCA) [8]. This DOD technique uses a piezoelectric
disc to cause a pressure wave that generates a spray of ink drops. This device was
never commercialized [9].
The first DOD technique that really emerged was developed by the Casio,
teletype and Paillard company in the 1960s; and is called the “electrostatic pull
inkjet“[10]. The basics of this technique are conductive ink held in a nozzle by
negative pressure. By application of a high voltage field the droplet could be
pulled out. Depending on the deflection field the droplet could be located on the
substrate.
Several companies developed printers with this technique but because of poor
print quality, the electrostatic pull principle was abandoned (but research on this
still exists).
Many of the DOD inkjet ideas systems available on the market today were
invented and developed in the 1970s and 1980s and generally the basis of
piezoelectric inkjet is attributed to three patents in the 1970s; one by Zoltan of the
Clevite Company in 1972 [11], one by Stemme of the Chalmers institute of
technology in 1973 [12] and one by Kyser and Sears of the Silonics Company in
1976 [13].

4
2.2. Inkjet ink
Digital printing using inkjet technology puts heavy demands on the physical
properties of the ink.
When a droplet strikes a surface it starts to spread, partly penetrates the paper
and evaporates Figure 3.
Surface tension and viscosity of the ink are important parameters affecting the
drop formation and the spreading of the droplet on the surface [14].

Figure 3. The printed dot is a result from spreading of the drop, evaporation
and penetration of the ink into the substrate.

There are three main types of inkjet inks: aqueous, non-aqueous (oil/solvent)
and phase- changing inks (hot melt/UV curable).
The main components of an aqueous/solvent based inkjet ink are carrier fluid
(~35-80%), humectants (~10-30%), surfactants and additives (~2-5%) and colourants
(~2-8%) [9].
The colourants in an inkjet ink can either be dyes fully dissolved in the solution
or pigments dispersed in the solution.
Different printing techniques use different inks and the drying mechanisms
differ between the types of ink [15]. Different ink types and drying mechanism for
the type of ink are presented in Table 1.

Table 1. Different ink and drying mechanisms

Ink Drying mechanism
Aqueous Absorption/Penetration
Evaporation
Oil Absorption/penetration
Solvent Evaporation
Hot melt Solidification
UV curable Polymerization

5
2.3. Inkjet paper
A paper for inkjet printing consists of chemical pulp (e.g. hardwood and
softwood fibres with varying shares and beating), fillers (typically calcium
carbonate from chalk or marble as Ground Calcium Carbonate (GCC) or
Precipitated Calcium Carbonate (PCC), starch, internal sizing and surface size to
control porosity and absorption, retention chemicals (to retain fillers, fines and
other additives) and FWA (Fluorescent Whitening Agent) [16].
Paper properties are affected by both the composition of the paper and by the
manufacturing process.
Some important properties for an inkjet paper are:
 
  
   
   
 
    
 
   absorption)
  
Each parameter is important for printability and runnability.
The main component of paper is fibres, usually from wood, cotton or grasses
[16]. The wood used in paper pulp is divided into two categories: “Hardwoods”
such as: oak, poplar, maple, birch, eucalyptus. (Short, soft, tubular and confer
bulkiness and formation properties) and “Softwoods”: pines, fur, spruce, etc. (long,
soft, flat with considerable strength but with less bulking and formation
tendencies). The fibres can be chemically or mechanically separated resulting in
different properties in the final product.
Uncoated office papers are often used for inkjet printing of text or when the
requirement of image quality is low.
To improve the print quality a coating layer consisting of binders, (starch and
latex) and pigments (kaolin or calcium carbonate) can be added onto the paper
surface [17].
When high quality papers are wanted, several coating layers can be added on
top of the paper surface. An example of inkjet coated paper is depicted in Figure 4
(drawn after [17]).

6
Figure 4. A high quality inkjet paper can have several layers of coating.

3. THEORY

3.1. Paper Optics

3.1.1. Light and colour
Light can be described both as a particle and as a wave; the wave-particle
duality. When we talk about light we often refer to the electromagnetic spectrum
that is visible to the human eye (380-770 nm), but it can also refer to other forms of
electromagnetic radiation, such as infrared and ultraviolet light.
White light includes all wavelengths. An object that absorbs some part of the
visual spectrum and reflects some appears coloured for a human eye.
The appearance of a coloured object mainly depends on the spectral power
distribution of the reflected light and on the surface characteristics of the object,
but also on surrounding colours, observing geometry and state of chromatic
adaption [18].
An uncoated paper has a fairly rough surface whereas a coated paper for inkjet
can have a matt or glossy surface. Depending on the smoothness of the surface, the
incident light can be more or less specular reflected (glossy surface) or diffuse
reflected [19].
Inside the paper bulk, the light can be reflected, refracted or diffracted to colour
pigments, filler, fibres etc. Figure 5:1-3 illustrates reflection, refraction and
diffraction

7
Figure 5:1. When light hits the surface or particles inside the bulk material it can
be reflected in different directions.

Figure 5:2. As light passes from one transparent medium to another it changes
speed, and is refracted. How much depends on the refractive index
of the mediums and the angle between the light ray and the line
perpendicular (normal) to the surface separating the two media.

Figure 5:3. When a light wave interacts with a single particle that is as large as
or smaller than the wavelength of light, the wave is diffracted. The
particle scatters the incident beam uniformly in all directions.

Molecules can absorb and emit packets of electromagnetic radiation. Different

molecules absorb radiation of different wavelengths due to the discrete energies
dictated by the detailed atomic structure of the atoms; this is the mechanism of
how colour is created for dye based ink.

8
3.1.2. CIE L*a*b*

In 1931 The Commission Internationale de l’Eclairage (CIE) introduced

standard illuminates, the colour matching functions and the device independent
tristimulus values. The aim of this was to get a uniform description of colours and
light sources [20].
In1976 CIE introduced the CIELAB colour space. The CIELAB colour space
takes the light source/object/human observer set of factors into account to the
colour matching functions and to the tristimulus values.
The CIE L*a*b* forms a Cartesian, approximately perceptual uniform colour
space, with the lightness coordinate L* (0 is black and 100 is white) and green-red
coordinates a* (-a* = greenness and +a* = redness) and blue yellow b* (-b* =
blueness and +b* = yellowness) [21]. Figure 6 illustrates the CIE L*a*b* colour
space.

Figure 6. CIELAB is a pseudo-uniform colour space that is defined by L* a*

and b*. L* represents the lightness, a* represents red to green axis
and b* represents blue to yellow axis.
The distance between two points in L*a*b* space is "# $"&'" <  >
to compare differences between two samples.
The Cartesian coordinates can be expressed in cylindrical coordinates, with the
hue defined as the angle and the chroma as radius. CIE 1976 L*a*b chroma is
defined as: C*ab=(a*2+b*2)1/2 and CIE 1976 hue angle: hab=arctan(a*/ b*)

9
3.2. Wetting and spreading
When a droplet hits a surface, it can spread to increase the surface between the
solid/liquid phase and the liquid/gas phase. The droplets can wet the surface
depending on the physical properties of the liquid and of the substrate. Wetting
means that the contact angle between the liquid and the substrate is very small so
that the liquid spread over the entire surface [22].
During inkjet printing, a limited amount of liquid is deposited onto a paper
surface. When the droplet hits the surface it starts to spread and wet the surface
depending on the ink and paper properties.

3.2.1. Contact angle

Contact angle is a function of energy of adhesion (between molecules in the

liquid and solid) and cohesive energy (between the molecules in the liquid. Strong
adhesion and weak cohesion leads to a low surface tension and small contact
angle, resulting in a high wetting.

Figure 7. Contact angle is a measure of how the liquid wets the surface.
When a droplet hits a surface, the contact angle goes from larger values to
smaller values until state of equilibrium has been reached. If the contact angle is
higher than 90 degrees, no wetting of the surface will occur.

3.2.2. Surface energy/ Surface tension

Surface energy is defined as the free energy required creating a surface, i.e. the
energy that must be added to increase the surface one area unit [23].
Surface tension can be described as the force per unit length that opposes the
expansion of a surface, or as the energy per unit area. The two are equivalent, but
in general, the term surface energy is applied to solids and the term surface tension
is applied to liquids.
One method for calculating surface energy is to use static contact angle
measurements together with Young’s equation and the work of adhesion based on
the Geometric Mean model.

10
 Young’s equation describes the relation between the surface energy and contact
angle for a liquid on a solid surface (where the spreading pressure of the liquid’s
vapour on the solid is negligible), equation (1) [23].

 =  +    (1)

SV is the surface energy of the solid, LV is the surface tension of the liquid, and SL
is the interfacial tension between solid and liquid.  is the contact angle between
the solid and the liquid.

The work of adhesion, Wa in general terms, the thermodynamic energy of

interaction, is given by equation (2).

=  +   (2)

Combining eq. (1) and (2) yields

=  (1 +  ) (3)

The surface energy of a material can be divided into different parts, corresponding
to various contributions from different interactions:

 =  +  (4)

where ?P corresponds to the polar component of the surface energy and ?D

corresponds to the non-polar (dispersive) component of the surface energy.

The work of adhesion based on the Geometric Mean model yields:

 
=  (1 +  ) = 2[(   )  + (   ) ] (5)

Since the polar component of diiodmethane is zero, the dispersive energy of the
solid can be determined by using data from measurements with diiodmethane,
equation (3) and equation (5). The disperse energy of the solid can be expressed in
terms of:


 = () (1 +   )

(6)


By using data from contact angle measurements with water and eq.5, the work
of adhesion can be expressed as:

11
  
   
= ( ) (1 +    ) = 2[( )    + ( )    ] (7)

Rearranging terms:


(( ) (1 +    ))   
 (( )   )

2 (8)
 = 
( )
By using equation (4), (6) and (8), the Surface energy for the substrate,  can be
expressed as:

(( ) (1 +    ))   
1  (   ) 
2 ( )
 = (() (1 +   ) 
4 ( )
(9)

3.3. Absorption
Inkjet printing on paper can be described physically as a process of deposition
of a finite amount of liquid into a porous structure and the print quality is directly
associated to the imbibition process [24].
During the last few years, several studies have been made on droplet dynamics
on porous substrate [25-37].
One theory describing fluid dynamics into capillaries is the Lucas-Washburn
equation [38-39].

3.3.1. Lucas-Washburn equation

The first study on the movement of water and of aqueous solutions through
paper and soils were made by the Bureau of Soils, U.S. department of Agriculture
in 1905 [40]. Following equation was proposed.

!" = #  $ (10)

where Y represents the distance through which the liquid has moved in the
time t, and n and K are constants dependent on temperature and specific
substrates.
In early 1900 Bell and Cameron analyzed the imbibition rate and found that the
imbibition follows the square root of time [41]. Bell and Cameron made this study
by using the Poiseuilles equation for laminar flow and equation (10)

! = #  $ (11)

12
 In 1918 Lucas [38] made studies to verify this square relation (eq. 11). Lucas
made experiments with glass tubes and filter papers.
Not aware of Lucas work, Washburn (1921) made similar research on
horizontal and vertical capillaries [39].
The Lucas-Washburn equation describes penetration of liquids into cylindrical
capillaries in the absence of a gravitational field.

Washburn applies Poiseuille's law for fluid motion in a circular tube according
to eq. 12.

' *, (12)

%& = (.  + 4/ 0 )%$
8-  %($)

dV describes the differential volume of the liquid that flows during the
differential time, dt, is the viscosity of the fluid, 3     $ 'Q is
the total effective pressure acting to force the liquid into the capillary which is the
sum of the participating pressures, such as the atmospheric pressure, the
hydrostatic pressure and the equivalent pressure due to capillary force. r
represents the radius of the capillary.
Under the assumption that the coefficient of slip is zero for wetting materials
and for capillaries so small that the external pressure can be neglected, the
penetration depth according to Lucas-Washburn, dLW(t), can be expressed as
proportional to the square root of time.
:;<>
%5 ($) = 65 7$ = 9 7$ (13)
?

where  represents the surface tension of the liquid and  represents the contact
angle.

13
4. METHODS AND MEASUREMENTS

4.1. Color meaurements

Spectral measurements made in this thesis were made by using a Gretag
Macbeth spectrophotometer (Figure 8). The measurement geometry of this device
is 45°/0° and it can be used with different physical filters, such as: D65
(approximated daylight), pol. (polarised) and without filter.

Colorimetry calculations can be made by using Spetrochart software with

different Illuminants: D50, D65, A, C, D30… D300, F1…F12 and with 2° or 10°
degrees of standard observer angles:

Figure 8. Gretac spectrophotometer measuring the spectral reflectance.

4.2. Line quality

Line quality is a measure of lateral spreading of ink onto the paper surface.
Scanner evaluation of printed lines can be made by using a flatbed scanner to scan
the lines and evaluation can be made by using image analysis.

In this thesis MATLAB® was used to analyse the images. The scanned images
were converted into grayscale values and the maximum and minimum reflectance
was used to calculated raggedness, blurriness and line width in accordance to the
ISO-13660 method.
A lower raggedness, less blurriness and smaller line width indicate lower
spreading of the ink and greater sharpness in the image.

Raggedness
Raggedness is a measure of edge unevenness of the printed line. Calculations of
raggedness were made by taking the contour of the printed line (extracted by using

14
the threshold value T60, corresponding to 60% of the maximal intensity in the
image).
The position of the ideal smooth line was calculated and the raggedness was
defined as the standard deviation of the distance d from the contour to the smooth
line. A description of raggedness is depicted in Figure 9.

Figure 9. Raggedness is a measure of edge unevenness of the printed line.

Definition of the raggedness is made by calculating the standard
deviation between the edge contour and the ideal smooth line.

Line width
Evaluation of the line width was made by calculating the mean value of the width
by using the threshold value 50% of the maximum intensity in the image. An
illustration of the line width has been depicted in Figure 10

Figure 10. Illustration of line width.

15
Blurriness
Blurriness is another measure of edge unevenness of the printed line.
Calculations of blurriness were made by calculating the mean width of the edge
zone defined as the part of the line with intensity in the range 1/3-2/3 of the
maximum intensity range.

4.3. Perception study

Visual judgment of an image is an important tool in print quality evaluation
[42]. There are various methods to perform perceptual studies, each one has its
advantages and disadvantages.
Before making a visual judgment of an image it is important to plan the setup
[42]. Selection of observers, samples: size and selection, and image content, number
of samples, time for each sample viewing distance, illumination and surroundings
and sample presentation are important parameters influencing the outcome of the
study [42].
The perception study made in this thesis was used to assess small differences in
detail reproduction between different samples in an image without being
influenced too much of the differences in print density between the images.
Because of the small differences in the images the 2-0 method was used.
Participants in the study were people working at paper mills and researchers
within paper and printing. The observers in the test panel were selected because of
their experience of paper and print, in order to be able to judge small differences in
the images.

4.4. Surface characteristics

4.4.1. Surface tension and Contact angle measurements
Measurement of surface tension of the ink and contact angle measurements in
this work were made with Fibrodat 1100 and the Pendant droplet method/sessile
drop.
4.4.2. Porosity
The characterisation of porosity was made by using mercury porosity
measurements and also the Bendtsen method using air leakage through the paper.
Mercury porosimetry was measured in an Autopore IV 9500 from Micrometrics
according to ISO/WD 1590-1.
4.4.3. Surface roughness
Surface roughness were characterised with the Bendtsen method using air
leakage at the paper surface (with a glass plate on the back side of the paper
sample).

16
4.4.4. Absorption of picolitre size droplets into papers
A high speed camera was used to capture film sequences of a droplet printed
onto a paper. A Matlab routine was used for image analysis. The method is
described in detail in paper IV.

17
5. SUMMARY OF THE PAPERS

The papers included in this thesis focus on dynamics and interactions between
inkjet inks and fine paper related to print quality.
Paper I addresses the effect of different variations in paper composition on
printouts made with SoHo printers and can be seen as an overview/ introduction
to this work. Paper II-III describes the effect of using salt for surface treatment on
fine paper before printouts made with pigmented ink. Paper II shows the effect on
detail reproduction whereas paper III examines the pigment aggregation on a salt
treated surface.
An experimental study of fluid dynamics of an inkjet droplet has been made in
Paper IV. Different paper properties such as surface roughness, porosity and
apparent surface energy have been measured and related to the absorption
process. The Lucas-Washburn equation has been tested and fitted to experimental
data.

5.1. Paper I
In this paper, the effect of different paper composition on inkjet print quality in
desktop printers has been studied. The background to this work was to improve
the physical paper-properties such as cockle and waviness without reducing the
print quality. Here the aim was to investigate how different paper composition in
terms of level of filler, internal sizing, level of beating, levels of hardwood fibres
and type of pulp affects the print quality for printouts made with SoHo (Small
office/Home office) printers.
Nine pilot papers produced in a small paper machine (lab-scale) with different
level of filler, internal sizing, hardwood content and levels of beating were used
and compared with eight commercial papers. The commercial papers were two
different high-speed inkjet papers, two different inkjet coated papers, and
copypaper with and without COLORLOK®.
Printouts were made in two different SoHo printers: one printer using
pigmented, water-based ink and one printer using dyes in water-based ink. The
print quality measurements were line quality measurements and colour gamut
measurements.
The result showed that paper composition variations (in a specific window) in
hardwood content, filler content and type of pulp did not affect the line quality or
colour gamut in an important way. It was found that an increased amount of filler
slightly decreases the colour gamut volume and low beating of the fibres worsened
the line quality.
Among the commercial paper, it was observed that COLORLOK® gave a high
colour gamut for pigmented ink and a low colour gamut for dye-based ink. Most

18
of the high speed inkjet papers exhibited a larger colour gamut than the pilot
papers and the standard copy paper in the case of pigmented inks.

5.2. Paper II
The purpose of this work was to determine the influence of different levels of
colourant fixation of a paper in a final printout. The colourant fixation used in this
study was calcium chloride solution added in the surface sizing and the printouts
were made in a desktop printer using pigmented, water based ink.
Both commercial papers with and without colourant fixation and trial papers
were used. The trial papers were uncoated, surface sized papers produced in the
same production run in a full scale paper machine. The only parameter that was
varied among the trial papers was the level of salt.
Print quality evaluation was made objectively by measuring edge sharpness
CIE L*a*b chroma and dot gain. Subjective measurements were made in perceptual
studies.
It is known that an increased level of colour fixation affects the print density. To
separate the results on detail reproduction from the variations in print density two
additional samples were therefore added to this study. One sample was created to
resemble a printout with the same print density as the sample with a low level of
colourant fixation, printed out on a paper with a high level of fixation. The other
sample was made by adding a Gaussian blur filter, to create a blurred image
printed out on a paper with a high level of fixation, i.e. high print density.
The perceptual study was made in three different laboratories with controlled
illumination and the judgment was made in a pair-wise comparison.
This study showed that the detail reproduction in a printed image is an
interplay between the print density and the edge sharpness originating from the
surface spreading of the droplet.
The results showed that an increased level of colourant fixation slightly reduces
the droplet spreading resulting in a higher detail reproduction. An increased level
of colourant fixation also increases the print density resulting in a higher detail
reproduction.

5.3. Paper III

In this paper, print quality in terms of detail reproduction and chroma for
papers with and without colourant fixation has been related to surface properties
for paper such as surface roughness, porosity and hydrophobicity.
The main purpose of this study was to investigate if high levels of salt can lead
to aggregation of pigments on the paper surface before printing making the
pigments stay closer to the surface. The papers and printer used in this work was
the same as used in paper II.

19
 SEM analyses have been used to study the printed surface and a light
microscope was used to study cross section images of the ink penetration into
paper.
Results show that salt as colourant fixation fixates the pigments close to the
surface resulting in better detail reproduction chroma and higher print density. It
also affects the ink stability making the pigments aggregate on the surface. The
aggregation of pigments might explain the smaller droplet spreading on the paper
surface resulting in a better detail reproduction.

5.4. Paper IV
This paper describes absorption of inkjet droplets into different paper qualities.
The aim was to study the fluid dynamics during the absorption process and
compare theoretical models to experimental data and relate the result to paper
properties.
Papers used in this work were selected papers among the pilot papers and
commercial papers used in paper I.
Inkjet droplets of dyes were printed out from a KODAK Versamark D5240 print
head and images were captured by using a high speed camera and 2000 fps. Paper
properties such as surface roughness, porosity and apparent surface energy were
measured and related to the result from the absorption study.
The results showed that a paper containing internal sizing had a lower apparent
surface energy, resulting in a smaller droplet spreading radius. The rate of
absorption of ink into an internal sized paper was slower compared to an unsized
paper. Evaporation played an important role in the absorption process for
internally sized papers.
The Lucas-Washburn equation for describing the penetration depth was tested
and compared to experimental data. It was found that the time dependence in the
Lucas-Washburn (L-W) equation was in the accordance with experimental data
whereas the L-W equation overestimated the penetration depth and the absorption
speed.

20
6. CONTRIBUTION TO THE THESIS

This thesis contributes to the inkjet printing area and the main part of the
results is directly related to the printing and paper production area. The study of
dynamics in terms of liquid penetration and flow into paper as porous substrates is
directly related to the high-speed printing area.
The overall contribution is to gain an increased knowledge in the field to be
able to produce high quality ink receptive substrates.
In this section the contribution to the thesis and the novelty of the listed papers
is described together with the contribution of the author of the thesis to each paper.

6.1. Paper I
This paper shows that variations in paper composition (in a certain window) for
uncoated pilot papers did not have a major impact on the print quality for
printouts made with SoHo printers. This leaves the opportunity to continue to vary
the surface treatment to improve the print quality for inkjet printing with SoHo
printers.
The paper samples used are the result from cooperation between the authors
and the project partners with the aim of producing papers with good runnability
and print quality.
This paper is the result of cooperation with Dr. Jonas Örtegren and Elisabeth
Alfthan. The contribution of the author of this thesis was part of the experimental
planning and main part of printing, measuring and analysis of color gamut and
line quality and presentation of the material and writing.

6.2. Paper II
This paper shows that the print quality for uncoated copy papers can be
improved by adding colourant fixation to a paper without changing the paper
composition.
The final result from this work showed that the detail reproduction in a final
printout is an interplay between print density and surface spreading of the droplet.
This paper is the result of cooperation with Dr. Ole Norberg, Kristina Wågberg
and Dr. Jonas Örtegren. The contribution of the author of this thesis was part of the
experimental planning and main part of printing, measuring and analysis of CIE
L*a*b* chroma and line quality, measuring and analysis of dot gain and analysis of
data from the perception study and presentation of the material and writing.

21
6.3. Paper III
This paper points out one of the effects of surface mechanism on print quality,
namely aggregation of ink pigments on the paper surface.
Printouts made with water-based ink have been studied on papers with
different concentrations of salt as colourant fixation.
The final results show that the ink stability can be affected by adding calcium
chloride as colour fixation making the pigments start to aggregate on top of the
surface.
The results also show that the aggregation of ink pigments improves the detail
reproduction and increases the CIE L*a*b* chroma.
This paper is the result of cooperation with Dr. Ole Norberg and Dr. Jonas
Örtegren. The contribution of the author of this thesis was part of the experimental
planning and main part of printing, measuring and analysis of print quality,
analysis of SEM imaging and presentation of the material and writing.

6.4. Paper IV
This paper describes the fluid dynamics of dye based ink into paper. The results
show how surface energy, surface roughness and porosity affect the absorption
rate, and droplet spreading of inkjet droplets on paper. It is also shown that the
Lucas-Washburn equation can be used in some extent to describe the absorption
process during printing.
This paper is the result of cooperation between Dr. Jonas Örtegren, Prof. Göran
Ström and Elisabeth Alfthan. The contribution of the author of this thesis was part
of the experimental planning and main part of printing, developing and testing
software for analyzing the droplet absorption as a function of time, adapt L-W
parameters from measurement and analysis of how well they fits to the
experimental results and presentation of the material and writing.

7. DISCUSSION AND FUTURE WORK

The main advantages with digital printing are the possibilities to variable
printing and profitability in short runs. The challenge with inkjet printing is to find
an ink receptive substrate that rapidly absorbs the carrier liquid and fixates the
colourant to the surface.
This work investigates the interaction between inkjet paper and ink. The aim
was to get an increased understanding in what mechanisms affect the print quality.
Digital printing in SoHo printers uses extremely small droplets (~1-4 pl.).
Printouts made with SoHo printers in Paper I did not show significantly large
differences in print quality for papers with different composition. However a low

22
degree of beating worsened the line quality. The results can be discussed in terms
of small spreading of the small droplets on the surface. For these small droplets
sizes, the surface spreading is low; independent of paper surface characteristics
and in the production process of pilot papers, the process differs from a full scale
production paper machine in terms of production speed resulting in more porous
paper. This might explain the small differences in print quality between the pilot
papers.
In paper I it was also shown that among the commercial papers, the copy paper
COLORLOK® reproduced a high colour gamut volume compared to the other
commercial uncoated papers for printout made with pigmented inks, (not with
dyes). In the patent literature, the COLORLOK® has been describes as a method to
improve the print quality by adding metallic salt on the surface treatment before
printing to affect the ink stability for printouts made with pigmented ink.
Pigmented ink often contains anionic dispersants to stabilize the ink and to avoid
undesirable aggregation of particles. By adding metallic salt to the paper surface it
might be possible to change the ink stability, by shielding the repulsive forces that
stabilizes the ink. This can make the pigments to aggregate faster.
In Paper II-III research has been made with bivalent salt at different
concentrations, to see how CMC can affect the print quality in terms of detail
reproduction. The reference paper in paper II-III contains mono-valent salt. To be
able to verify the DLVO theory, the CMC should be reached by added a high
concentration of monovalent salt.
Suggestion for future work would be to study the print quality and aggregation
of pigments by using mono, di-and trivalent salt and different types of model ink
with known composition.
One important parameter during inkjet printing at high-speed is the absorption
speed. Low absorption speed can lead to colour to colour bleeding and low
sharpness. In this work (paper IV) it has been shown that hydrophobic character of
the paper plays an important role for the absorption speed when printing is made
with picolitre sized ink droplets. Adding internal sizing to the paper strongly
reduces the absorption process compared to an unsized paper.
The L-W time dependent in the L-W equation was fairly well fitted to data,
whereas the overall equation overestimates the results. The L-W equation was
derived for an absorption process in an infinite cylindrical tube and this might not
be the right model for describing absorption into paper as porous material. Paper
can be described as an inhomogeneous porous network of fibers, filler etc. The L-W
equation describing a fluid in a cylindrical tube fails in this case, due to the
complexity in the paper fiber network.
To be able to separate the mechanisms, i.e. how the porosity affects the
absorption, homogenous model substrate should be used.

23
8. CONCLUSIONS

This thesis sums up some of the mechanisms that can occur during inkjet
printing and affect the print quality. The result is directly applicable to paper and
print industry.
The result showed that there are small variations in print quality for printouts
made with desktop printers on uncoated pilot papers with varying composition (in
a specific parameter window). This leaves the opportunity to work with
parameters to improve runnability without affecting the print quality in an
important way.
The detail reproduction and the print density for printouts made with pigment
containing inks can be improved by adding color fixation onto a paper before
printing. Adding a solution with calcium chloride as colourant fixation can lead to
aggregation of the pigments and reduce the ink penetration.
The detail reproduction in a printed image is an interplay between the print
density and the edge definition originating from surface spreading of the droplets.
Internal sizing in the uncoated papers lowers the apparent surface energy, the
droplet spreading and the rate of ink absorption. Evaporation played an important
role in the absorption process in the case of internally sized, uncoated papers.
The Lucas-Washburn (L-W) equation overestimated the penetration depth and
the speed at which the pores are filled, but it was found that the time dependence
in the L-W equation was in accordance with experimental data for absorption of an
inkjet droplet into a paper.

24
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