available online @ www.pccc.icrc.ac.

ir
Progress in Color Colorants Coating 18 (2025), 177-188

Optimizing the Surfactant/Polymeric Dispersant Combination in Pigment-Based

Aqueous Inkjet Inks
M. Jalili*1, M. Mohammad Raei Naeini**1, S. Bastani1,2, N. Ajili1
1 Department of Printing Science and Technology, Institute for Color Science and Technology, P.O. Box: 32465-654,
Tehran, Iran.
2 Department of Surface Coating and Corrosion, Institute for Color Science and Technology, P.O. Box: 32465-654,
Tehran, Iran.

ARTICLE INFO

Article history:
igment-based inkjet printing offers numerous advantages over
Received: 27 July 2024
Final Revised: 20 Sept 2024
Accepted: 21 Sept 2024
P traditional contact printing techniques; however, these inks require
stringent dispersion properties and a delicate balance between
rheological behavior and surface tension. This study addresses these challenges
Available online: 23 Oct 2024
by exploring and optimizing the combination of surfactants and dispersing
Keywords: agents. We aimed to achieve a stable nanosized dispersion of Disperse Blue 359
Pigment dispersion in aqueous pigment-based inkjet inks while adjusting its rheological properties
Inkjet printing using a polymeric dispersant and surfactants. Various formulations with
Polymeric dispersant different surfactants and polymeric dispersant concentrations were assessed for
Surfactant rheological behavior, surface tension, particle size distribution, and dispersion
Interface stability. Among the assessed surfactants, the surfactant with the lowest
hydrophilic-lipophilic balance offered the lowest and most stable particle size. It
also showed the best performance during milling and almost Newtonian
rheological behavior. It was attributed to its higher tendency to absorb on the
particle surface. The optimization of polymeric dispersant concentration also
revealed that samples with too low dispersant, experience flocculation rapidly
after milling due to insufficient dispersant to cover the fresh surface of ground
particles. On the other hand, samples with too high dispersant concentration
have stability issues and also non-Newtonian rheological behavior because of
too thick absorbed layer of dispersant on the particle surface and high
concentration of non-absorbed polymer chains in the media. The optimized
combination resulted in a stable nanosized pigment dispersion with low viscosity
and Newtonian behavior. These findings provide valuable insights into
formulating high-performance pigment-based inkjet inks, highlighting the
critical interplay between dispersants and surfactants in achieving optimal
performance. Prog. Color Colorants Coat. 18 (2025), 177-188© Institute for
Color Science and Technology.

enormous advantages over traditional printing

1. Introduction
methods. As a non-contact technique, inkjet printing
In recent decades, inkjet printing inks have been under offers several benefits, including reduced complexity,
the limelight by various researchers owing to their smaller and less sophisticated printing machines,

*Corresponding author: * Jalili @icrc.ac.ir

** [email protected]
https://doi.org/10.30509/pccc.2024.167361.1316
 M. Jalili et al.

no need for pretreatment, and most notably, the the particles and reduce the milling time required to
absence of stencils or plates. These features confer achieve appropriate particle sizes, while also helping to
substantial superiority in terms of customization. adjust the surface tension of the ink [23, 28-30]. While
Unlike traditional contact printing methods such as the presence of surfactants and polymeric dispersants
offset and gravure, inkjet printing can produce any is crucial for achieving an optimal dispersion state,
desired print job, regardless of the print run size, their interdependence complicates the dispersion and
making it highly versatile and efficient for customized stabilization of pigment-based inkjet inks, as they
and short-run printing tasks. Additionally, inkjet affect one another's performance.
printing generates less waste and has a lower In addition to the particle size of pigments and their
environmental footprint. Collectively, these advantages stability in the ink, the overall performance of inkjet
position inkjet printing robustly in various rapidly printing inks heavily relies on the interplay between
growing markets. For instance, the compound annual rheological behavior and surface tension, both
growth rate (CAGR) of inkjet inks in the textile significantly affected by polymeric dispersants and
industry is forecasted to reach 17.5 % from 2024 to surfactants. Accordingly, it is believed that the
2029, clearly showing its brilliant perspective [1-9]. printability of ink can be roughly predicted by
Inkjet inks are divided into two types based on the considering its Weber number (We), which relates to
colorants used: dye-based and pigment-based inks. surface tension, and its Reynolds number (Re), which
Although dye-based inks continue to dominate some describes flow behavior. Therefore, the development of
applications, pigment-based inks have progressively pigment-based inkjet inks must ensure that rheological
expanded their market share since the late 1980s, behaviors and surface tension meet the stringent
particularly in response to the growing need for better requirements for inkjet inks [31-34]. This complexity
light and wash fastness in inkjet-printed items [7]. arises from the inevitability of incorporating surfactants
However, formulating pigment-based inkjet inks is and polymeric dispersants, which not only directly affect
more demanding, as it requires highly stabilized, low flowability and surface behavior but also influence these
particle size dispersion of pigment particles in the ink characteristics by modifying the state of dispersion.
medium. Maintaining particle size during application Particle size distribution and interparticle interactions
and storage is crucial to prevent clogging of the tiny significantly influence the rheological properties and
nozzles and channels [7, 10]. Given the small size of surface tension characteristics of the ink. Both the
these nozzles and channels, it is widely recognized that molecular structure and quantities of dispersants and
the particle size of pigment-based inkjet inks should be surfactants in the formulation influence the overall
less than 450 nm, and preferably below 200 nm, after performance of the ink [35-37].
production, during storage, and application. This The effects of polymeric dispersant and surfactant
requirement can be fulfilled by surface modification of combinations on the properties of aqueous pigment-
the pigments, either chemically [11] or physically [12- based inkjet inks have been thoroughly scrutinized to
14]. address these issues. Different surfactants and various
Polymeric dispersants play a vital role in dispersing polymeric dispersant concentrations have been studied
and stabilizing pigment particles in the ink medium to achieve proper dispersion of Disperse Blue 359, a
via physical modification approach [15-19]. These well-known pigment for sublimation transfer inkjet
macromolecules contain pigment-affinic groups, or inks, while maintaining the formulation's flowability
anchors, that attach to the particle surfaces, while and surface tension within appropriate ranges for inkjet
soluble segments in the media create electrostatic applications.
repulsion or steric hindrance, preventing particle
agglomeration [20-27]. Although polymeric dispersants 2. Experimental
provide essential stabilization for dispersed particles,
2.1. Materials and instruments
their high molecular weight results in slower
absorption onto the particle surfaces. Conversely, DISPERBYK® 2015 (PolyD2015), a 40 wt.% aqueous
surfactants, being smaller molecules, are kinetically solution of modified styrene-maleic anhydride
more favorable for absorption onto the pigment copolymer was purchased from BYK company. Oleic
surface. They are added to improve the wettability of acid ethoxylate (6 moles, KEOL6), oleic acid

178 Prog. Color Colorants Coat. 18 (2025), 177-188

Optimizing the Surfactant/Polymeric Dispersant Combination in …

ethoxylate (9 moles, KEOL9), and nonyl phenol phase, the impact of various surfactants on the milling
ethoxylate (10 moles, KENON10) were all provided by process and milling paste characteristics were
Kimyagaran Emrooz company. Disperse Blue 359 investigated. Mill base formulations with different
(D.B.359) was supplied by Tiankum Company. surfactants were prepared, as detailed in Table 1. The
Ethylene glycol (99.5 %), glycerol (99.5 %), and mill base preparation involved dissolving the appropriate
propylene glycol (99 %) were obtained from Merck amounts of polyD2015, surfactant, and propylene glycol
Company. in deionized water using a magnetic stirrer. Once
Surface tension measurements were conducted with complete dissolution was achieved, D.B.359 was
a Kruss tensiometer using the Wilhelmy plate method. gradually added to the stirring solution, and stirring
Particle size distribution was measured using the continued for an additional 60 minutes to ensure
Horiba SZ-100 instrument. Rheological properties thorough wetting of the dye particles. Subsequently, 25 g
were evaluated using the MCR300 Physica Anton par of the mill base was poured into the milling vessel along
with concentric cylinder, which enabled assessment of with 190 g of zirconia grinding media (0.8-1 mm
ink flow behavior and viscosity. The accuracy of diameter). Milling was conducted using a jar mill at 175
viscosity measurement was assessed, and the error rpm for 120 hours.
margin for rheological measurements was found to be Upon determining the surfactant with the best
less than 0.5 mPas. Turbidity measurements during performance, the second phase of the study aimed to
milling and storage were conducted with a Hach optimize the concentration of the polymeric dispersant.
2100N instrument, providing data on milling Accordingly, samples with the most efficient surfactant
effectiveness and ink stability during storage. The and varying amounts of polyD2015 were prepared based
accuracy of turbidity measurement was also assessed, on the formulations in Table 2. The nomenclature of
and the error margin was found to be less than 3 NTU. samples is based on the weight ratio of the solid
polymeric dispersant to the pigment. The mill base
2.2. Sample preparation preparation followed the procedure used in the first
This study was conducted in two phases. In the first phase of the study.

Table 1: Sample formulations for determining the proper surfactant.

Sample polyD2015 KEOL6 KENON10 KEOL9 Glycerol PG D.B.359 Water

name (g) (g) (g) (g) (g) (g) (g) (g)
Blank 2.5 – – – 1 1 2 6.25

Kl6 2.5 0.1 – – 1 1 2 6.15

Kn10 2.5 – 0.1 – 1 1 2 6.15

Kl9 2.5 – – 0.1 1 1 2 6.15

Table 2: Sample formulations for optimizing the dispersing agent content.

Sample name D.B.359 (g) polyD2015 (g) surfactant (g) Glycerol (g) PG (g) Water (g)

S-25 2 1.25 0.1 1 1 8.75

S-50 2 2.5 0.1 1 1 7.5

S-75 2 3.75 0.1 1 1 6.25

S-100 2 5 0.1 1 1 5

S-125 2 6.25 0.1 1 1 3.75

S-150 2 7.5 0.1 1 1 2.5

Prog. Color Colorants Coat. 18 (2025), 177-188 179

 M. Jalili et al.

3. Results and Discussions unabsorbed surfactant in the media and thus an

increase in surface tension. However, before milling,
3.1. The effect of surfactant nature
significant surfactant absorption does not occur on the
Various behaviors of inkjet inks during production, pigment surface due to its low surface area, leaving the
droplet formation, droplet transfer, and interactions with surface tension unchanged. Moreover, the surface
substrates are significantly influenced by surfactants. tension of the samples is also influenced by the
During the production of the mill base, surfactants lower intrinsic characteristics of the surfactants, as detailed in
surface tension, allowing the mill base media to Table 4.
penetrate the grooves and crevices of pigment Surfactants can greatly affect the kinetics of
aggregates and agglomerates. This enhancement in dispersion since they are kinetically more favorable
wetting improves the efficiency of the milling process than polymeric dispersants to absorb on the particle
and reduces its duration. Furthermore, better wetting surface owing to their low molecular weight.
minimizes interactions between suspended particles, Therefore, they greatly enhance surface wetting, the
which is reflected in the rheological properties. first step of dispersion. To find out which surfactant
Interparticle interactions lead to energy dissipation enhances milling kinetics more efficiently, the
during flow, causing the fluid to exhibit non-Newtonian evolution of sample turbidity during the milling
behavior. Consequently, the effects of various process has been monitored using turbidimetry.
surfactants on the surface tension and rheological Comparing the turbidity of samples with the same
behavior of mill bases have been studied to identify the pigment and concentration provides insight into their
most effective option [5, 38]. Measurements were taken particle size [36, 39-41]. Turbidity was recorded after
to examine how the surfactant structure and the milling 24 hours of milling, as indicative of the initial rate of
process affect the surface tension of the mill base (Table particle size reduction and after 120 hours as the
3). ultimate particle size reduction efficiency. As depicted
As shown, the addition of pigment to the media in Table 4, Kl6 greatly enhances the milling rate
does not significantly affect the surface tension of the compared with other samples. Given that Blank
samples unless milling occurs. Grinding the large exhibits the highest turbidity at the initial stage of
pigment particles during the milling process increases milling, it can be also deduced that all the surfactants
their surface area, allowing for greater surfactant improve the dispersion kinetics by enhancing the
absorption. This results in a lower amount of wetting process.

Table 3: Effect of surfactant structure and milling process on the surface tension of the mill base.

mill base before milling mill base after milling

Sample pigment-free media (mN/m)
(mN/m) (mN/m)
Blank 43.437 ± 0.5 43.491 ± 0.5 47.919 ± 0.5

Kl6 35.147 ± 0.5 35.217 ± 0.5 39.381 ± 0.5

Kl9 38.512 ± 0.5 38.630 ± 0.5 42.041 ± 0.5

Kn10 33.965 ± 0.5 33.841 ± 0.5 38.137 ± 0.5

Table 4: Turbidity evolution of samples with different surfactants during milling.

Sample Blank Kn10 Kl6 Kl9

Turbidity after 24 (NTU) 5384 ± 3 4671 ± 3 3232 ± 3 4246 ± 3

Turbidity after 120 (NTU) 1352 ± 3 1023 ± 3 565 ± 3 793 ± 3

180 Prog. Color Colorants Coat. 18 (2025), 177-188

Optimizing the Surfactant/Polymeric Dispersant Combination in …

The stability of pigment dispersion is also of great Dispersions with high interparticle interactions exhibit
importance. The particle size of samples during storage viscoelastic behavior, while those with minimal
time after milling was also assessed using turbidimetry. interactions display nearly Newtonian rheological
The turbidimetric evaluation was conducted to properties. Furthermore, reducing interparticle
investigate the stability of the samples after milling. In interactions in pigment dispersions leads to lower
this regard, the samples were stored after milling, and viscosity, which is critical for inkjet inks to ensure
their turbidity was measured over a prolonged time. proper droplet formation and transfer to the substrate
The changes in turbidity over time are represented in [45, 46]. Consequently, the rheological characteristics of
Figure 1. It can be seen that Kl6 has the smallest and the samples have been investigated.
most stable pigment particles, exhibiting the lowest A four-step testing approach was used to assess the
turbidity, which remains constant throughout the rheological behavior of the inkjet ink samples. To
storage period. Kl9 shows a nearly stable dispersion; eliminate residual rheological effects in the samples
yet, its higher turbidity than Kl6 suggests a larger from prior processes, every sample was first subjected to
particle size. Blank and Kn10 not only exhibit larger a pre-shear treatment. The pre-shear treatment includes
particle sizes, as indicated by their high turbidity but one minute of exposure to a shear rate of 100 s-1 which is
also exhibit stability issues, as reflected in their followed by two minutes of rest. This way, the viscosity
fluctuating turbidity over time. The decreasing of the samples at low shear rates as well as its stability
turbidity of Blank and Kn10 during storage can be over time have been assessed. After these two steps, a
attributed to the sedimentation of pigment particles, shear sweep test has been conducted in both loading and
which consequently reduces the concentration of unloading mode.
scattering particles in the samples. During the loading phase, measurements of the shear
The particle size of samples was also assessed using sweep were performed by gradually increasing the shear
turbidimetry. Comparing the turbidity of samples with rates from 0.01 to 1000 s-1 over one minute. This process
the same pigment and same concentration can give an enabled the evaluation of how the viscosity of the ink
insight into their particle size. The turbidimetric responded to escalating shear conditions. After the
evaluation was also conducted to investigate the loading phase, the unloading phase commenced, where
stability of the samples after milling. In this regard, shear rates were reduced from 1000 s-1 back to 0.01 s-1,
samples were stored after milling, and their turbidity also over one minute. This phase offered valuable
was measured over a prolonged storage time. The insights into the viscoelastic characteristics of the ink
turbidity changes of samples over time are represented and its capacity to revert to its original rheological state
in Figure 1. It can be seen that Kl6 has the smallest and after being subjected to high shear rates. [19, 29].
most stable pigment particles. It has the lowest
turbidity which remains constant over storage time.
Kl9 has almost stable dispersion however, its higher
turbidity in comparison with Kl6, denotes its larger
particle size. Blank and Kn10 not only have large
particle sizes, which is indicated by their high turbidity
but also, have stability issues which are depicted in
their deviating turbidity over time. The reducing
turbidity of Blank and Kn10 over storage time can be
attributed to the sedimentation of pigment particles,
which consequently reduces the concentration of
scattering particles in the samples.
The state of dispersion is reflected in the rheological
behavior. The layer of dispersing and wetting agents
absorbed on the pigment particles prevents flocculation
Figure 1: Turbidity evolution of samples with different
by reducing interparticle interactions, thereby stabilizing surfactants, during storage.
them in the media [42-44]. Limiting these interactions
also affects the fluid's response to applied shear forces.

Prog. Color Colorants Coat. 18 (2025), 177-188 181

 M. Jalili et al.

The viscosity of Newtonian fluids is independent of improved dispersion [47, 48]. As shown in Table 6, Kl6
time or shear rate. Consequently, at the initial stage of exhibits very low hysteresis, verifying its superior
rheological assessment, the viscosity at 100 s-1 over dispersion quality. Given that the hydrophilic-lipophilic
time was measured. As illustrated in Figure 2, Kl6 and balance (HLB) of KEOL6, KENON10, and KEOL9 are
Kl9 maintain stable viscosity at 100 s-1, while Kn10 9.9, 13.4, and 11.6, respectively.
and the blank sample exhibit significant viscosity
variations over time. Additionally, Kl6 displays the
lowest viscosity. The average viscosity at 100 s⁻¹ is
summarized in Table 5.
The rheological behavior of samples with various
surfactants in loading and unloading modes are shown in
Figure 3. As can be observed, Kl6 exhibits nearly
constant viscosity over various shear rates, while Blank,
Kl9, and Kn10 show shear thinning behavior (Table 6).
Rheological hysteresis represents the extent of
energy dissipation upon the flow of the fluids. It
describes the discrepancy in the behavior of viscoelastic
fluids during the loading and unloading phases of cyclic
strain sweeps, which stems from energy dissipation
caused by particle interactions. A lower rheological
Figure 2: Viscosity of samples with different surfactants
hysteresis signifies reduced particle interactions and
at 100s-1, over time.

Figure 3: Viscosity of the samples with different surfactants as a function of shear rate in (up) loading mode and (down)
unloading mode.

Table 5: Effect of surfactant on the viscosity at 100 s-1.

Sample Blank Kn10 Kl6 Kl9

Viscosity (mPa.s) 46.78 50.69 9.17 28.59

Table 6: Rheological hysteresis of samples with various surfactants.

Sample Blank Kn10 Kl6 Kl9

Rheological hysteresis 8221.11 6926.48 665.98 6062

182 Prog. Color Colorants Coat. 18 (2025), 177-188

Optimizing the Surfactant/Polymeric Dispersant Combination in …

It seems that the tendency of KEOL6 to remove from charge [50]. This can also lead to an increase in
the solution and absorb on the particle surface is higher unabsorbed polymer chains in the solution, which may
in comparison to the two other surfactants, which can induce depletion flocculation and further suppress steric
explain the lower hysteresis, lower viscosity, and more hindrance [51-53]. Conversely, insufficient amounts of
Newtonian behavior in Kl6 rather than Kl9 and Kn10. It polymeric dispersant can leave parts of the particle
can also explain the superior performance of KEOL6 surface uncovered, resulting in flocculation [53].
over other surfactants in enhancing milling rate (Table 4) Therefore, optimizing the dispersant concentration is
since it has more tendency to absorb on the particle crucial. To identify the optimal dispersant concentration,
surface and improve its wetting. samples with varying amounts of dispersant were
prepared. In all samples, Kl6, which has demonstrated
3.2. The effect of dispersant concentration superiority over the other two counterparts, was used as
In addition to the surfactant structure, the concentration the surfactant.
of dispersant significantly influences the performance of The influence of polymeric dispersant concentration
pigment-based inkjet inks. It is well established that on the dispersion of pigment in the media has been
excessive amounts of polymeric moieties in inkjet thoroughly analyzed. Particle size was first assessed
formulations can cause the system to transition from a using DLS. As shown in Figure 4, increasing the
dilute regime to semi-dilute and concentrated regimes, concentration of PolyD2015 up to 50 % of the pigment
leading to significant interactions between polymer reduces the particle size, while further increments lead to
chains. This is an undesirable situation for inkjet an increase in particle size. Incorporating PolyD2015 up
applications, as it can deviate their rheological to 75 % of pigment weight still keeps the particle size
performance from that of Newtonian fluids [49]. below 250 nm which is acceptable for inkjet inks;
Moreover, incorporating an excessive quantity of however, samples containing 100 % or more of
polymeric dispersant adversely affects the state of PolyD2015 exhibit bimodal particle size distribution,
dispersion by suppressing both electrostatic and steric with the first peak below 500 nm and a second peak
hindrance mechanisms that stabilize particles. A surplus larger than one micron. Finally, S-150 only shows a
of charge-bearing polymeric dispersants can form a thick peak in the micron range.
layer on the particle surface, neutralizing its surface

Figure 4: The effect of polymeric dispersant concentration on the particle size distribution and (inset) particle size in the
micron range.

Prog. Color Colorants Coat. 18 (2025), 177-188 183

 M. Jalili et al.

To understand the effect of polymeric dispersant on resemblance to Newtonian fluids. The rheological
the dispersion stability of the pigment, the turbidity of the hysteresis of this sample is also lower than others as
samples over prolonged storage time has been monitored. shown in Table 7, confirming the superior dispersion
The turbidity deviation of samples over time is quality of S-50 compared to the other samples. It is also
represented in Figure 5. As seen, the S-50 has the lowest noticeable that passing dispersant to pigment ratio above
and most stable turbidity over time. S-75 also shows low of 75 %, further incorporation of dispersant causes the
turbidity variation, indicative of its stability, however, its rheological hysteresis to decrease. It is in good alliance
turbidity is higher than S-50 which demonstrates its with DLS findings which confirmed the presence of
higher particle size. S-20 displays a markedly different large micron-size pigment clusters in these samples.
turbidity profile over time, with an initial turbidity Larger particle sizes in these samples provide smaller
significantly higher than that of S-50 and S-75. surface area and hence lower interaction between
Moreover, it exhibits a rapid increase in the first days of particles surfaces. It can explain their lower rheological
storage which is followed by a swift decrease. As the hysteresis in comparison with S-25 and S-75, in which a
milling proceeds, pigment aggregates, and agglomerates tiny coincidence of small particle size and appropriate
continue to break down, which provides a new, fresh dispersing agent concentration, causes significant
surface for dispersants and surfactants to absorb. If the interactions.
dispersant concentration is insufficient, some parts of the
surface remain uncovered and susceptible to flocculation.
Applied shear forces during milling can mitigate
flocculation tendencies, but in the absence of such forces
during storage, particles rapidly flocculate, leading to
increased turbidity. The flocculated particles eventually
precipitate, resulting in a significant decrease in overall
turbidity. In S-100, S-125, and S-150, different behaviors
are observable. In these samples, turbidity first starts to
reduce consistently at a considerable rate that can be
attributed to the precipitation of large particles-their
presence has already been indicated by DLS. This initial
steady decrease is followed by a rapid increase and then a
decrease in turbidity. It can be interpreted as the
Figure 5: Turbidity of the samples with various amounts
formation and then precipitation of particle flocculation
of polymeric dispersant, over time.
since, excessive polymeric dispersant deteriorates
dispersion stability by neutralizing particles surface
charge -which is the main stabilization mechanism of
PolyD2015- and depletion-induced phenomenon.
Dispersion efficiency is also well represented in
rheological behavior. The standard four-step rheological
measurement is carried out on the samples with various
dispersant concentrations as described earlier in this
article. The viscosity of the samples at the shear rate of
100 s-1 over time is represented in Figure 6. S-50
exhibits the lowest viscosity and also the highest
viscosity consistency over time. Increasing the amount
of dispersant causes the viscosity to increase gradually
from S-75 to S-150. It can be attributed to the rise up of
unabsorbed polymer chains in the solution. The
Figure 6: Viscosity of samples with various amounts of
rheological evaluation of the samples in shear sweeping polymeric dispersants at 100 s-1.
mode, in both the loading and unloading phase (Figure
7) further reveals that S-50 shows the highest

184 Prog. Color Colorants Coat. 18 (2025), 177-188

Optimizing the Surfactant/Polymeric Dispersant Combination in …

Table 7: Rheological hysteresis of samples with various amounts of polymeric dispersants.

Sample S-25 S-50 S-75 S-100 S-125 S-150

Rheological
4953.77 665.98 3708.2 2299.68 1342.09 1521.58
hysteresis

Figure 7: Viscosity of the samples with various amounts of polymeric dispersant as a function of shear rate in (up)
loading mode and (down) unloading mode.

Table 8: viscosity of samples with various amounts of polymeric dispersants at 1000 s-1.

Sample S-25 S-50 S-75 S-100 S-125 S-150

viscosity (mPa.s) 6.95 8.21 10.2 13.7 20 25.7

The viscosity of samples at 1000s-1 is also the particles, thus reducing their mobility. S-100, S-
represented in Table 8. It is evident that increasing the 125, and S-150 exhibit high viscosity and cannot be
amount of polymeric dispersant in the formulation, effectively ground in the jar mill, resulting in the
causes the viscosity to grow up. This trend has not seen presence of some larger, unground pigment particles.
at 100s-1 (Figure 7). It seems that at high shear rates, These non-ground particles contribute to the second
most of the interparticle interactions have been peak in their bimodal particle size distribution curves.
disappeared and only the interactions attributed to the
polymeric chains are remained, while at low shear 4. Conclusion
rates, interparticle interactions are predominant. The
In developing aqueous pigment-based inkjet inks various
higher viscosity of the samples at high shear rates can
issues have to be addressed, among which, dispersion
explain the presence of micron-size particles in the
and printability are paramount. Pigment-based inkjet
samples with excessive amount of polymeric dispersant
inks should have particle sizes of less than 250 nm and
which was revealed by DLS. Milling was carried out
maintain stability during storage and application.
using jar mill, a low energy milling method. The
Furthermore, obtaining optimum printability necessitates
milling efficiency of a jar mill is heavily dependent on
a delicate balance between rheological characteristics
factors such as jar size, rotation speed, media size,
and surface tension. This issue is challenging to
density, volume fraction of milling media, and the
overcome since dispersing agents and surfactants
viscosity of the mill base. High-viscosity mill bases
predominantly affect dispersion and simultaneously
impede the transfer of energy from the milling media to
interact and influence both rheological behavior and

Prog. Color Colorants Coat. 18 (2025), 177-188 185

 M. Jalili et al.

surface tension directly and through their effects on the shear which is the confirmation of its Newtonian
state of dispersion. rheological behavior. Furthermore, S-50 had the lowest
In pursuit of a scientific method for optimizing rheological hysteresis, all indicating minimal
polymeric dispersant/surfactant combinations in the interparticle interaction. S-25 on the other hand shows
formulation of aqueous pigment-based inkjet inks, very low dispersion stability but maintained sub-
various formulations have been developed. Among micron particle size. It also shows the highest
different surfactants, it was found that Kl6 provided the rheological hysteresis suggesting insufficiency of
best rheological behavior, which means low viscosity dispersant in this sample for covering the new surfaces
with the lowest dependency on either the size or duration generated during milling, leading to flocculation of the
of shear. It also exhibited the best performance on ground pigment particles.
improving milling kinetics and dispersion stability which Given their high viscosity and the presence of large
was verified by turbidimetry. The superior performance pigment clusters, samples with a dispersant to pigment
of Kl6 was attributed to its lower HLB and higher concentration above 75 % are considered too viscous to
tendency to absorb on the pigment surface. be properly milled by low-shear methods such as jar
The study then continued by exploring the optimal milling. The excessive amount of polymeric dispersant
polymeric dispersant concentration in the presence of in these samples likely shifts them from a dilute to a
Kl6. DLS showed that the tiniest particles with the semi-concentrated regime, which prevents the milling
most uniform distribution were obtained at a surfactant beads from effectively impacting and breaking the
to pigment ratio of 50 %. Sample with dispersant to clusters, leaving some agglomerates unground.
pigment ratio below 50 % had larger particle sizes Additionally, the excessive polymer dispersant not only
while ratios above 75 %, had bimodal particle size impairs the milling process by increasing polymer chain
distribution curves with a peak in the micron range. entanglement but also deteriorates the stability of the
Monitoring the turbidity over time indicated that S-50 dispersion through various mechanisms, as evidenced by
also exhibits the best dispersion stability over time. zeta potential and turbidimetry measurements. These
Rheological assessment confirms the superiority of findings shed light on how to formulate high-
S-50 in terms of the state of dispersion. The sample had performance pigment-based inkjet inks, emphasizing the
the lowest viscosity while its viscosity was almost interplay between dispersants and surfactants in
independent of the duration and size of the applied obtaining maximum printability and stability.

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How to cite this article:

Jalili M, Mohammad Raei Naeini M, Bastani S, Ajili N. Optimizing the Surfactant/Polymeric
Dispersant Combination in Pigment-Based Aqueous Inkjet Inks. Prog Color Colorants Coat.
2025;18(2):177-188. https://doi.org/ 10.30509/pccc.2024.167361.1316.

188 Prog. Color Colorants Coat. 18 (2025), 177-188