Final Progress Report of Major Research Project

Entitled

Design Modelling and simulation of stirred ball mill and

ultrasound assisted dispersion of nanopigments for
utilization in formulations of coatings, printing ink,
pharmaceuticals and cosmetics
(F. No. 40-11/2011(SR))
Submitted to

University Grant Commission, New Delhi

By

Mr. Tushar D. Deshpande

Assistant Professor
Principal Investigator-UGC MRP
University Institute of Chemical Technology,
North Maharashtra University Jalgaon (M. S.)
1. Introduction
Pigments are inorganic or organic particulate materials which are insoluble in polymeric
binders and physically and chemically unaffected by the vehicle in which they are
incorporated. Pigments selectively absorb certain wavelengths of visible light and reflect the
rest of the wavelengths, which results in color appearance. The manufacture of paint
constitutes dispersion of particulate pigments in polymeric binder in presence of additives
and solvents using suitable dispersion machineries where a sufficient shear stress is imparted
to separate the pigment aggregates in the presence of a dispersion stabilizer. The dispersion
of pigment in polymeric binder in presence of additives and solvents is one of the most
expensive steps in manufacture of paint. High performance pigment production can be
accomplished by effectively controlling shape, particle size or surface of the pigment.
Successful grinding requires both effective particle capture and sufficient impact intensity
with optimum energy utilization. Generally, the influencing parameters for breaking up the
agglomerates in a dispersion process can be divided into the properties of the dispersed
particles, the formulation of the homogenous phase and the stress mechanisms, stress
intensity and stress frequency of the dispersing machine itself. Different dispersion
machineries such as kneader mill, bead mill, stirred ball mill etc utilize combinations of
different stress mechanisms for breaking of agglomerates. Consequently, every dispersing
machine has its own specific dispersing behavior [1]. Stirred ball mill has simple
construction; high size reduction rate and low wear contamination by which it can produce
fine and super fine material very effectively [2]. Owing to their high efficiency stirred ball
mills have replaced traditional system.

Conventionally particle size reduction and dispersion is being achieved by grinding in

equipments such as Ball Mill, Bead Mill using grinding media of specific size, geometry and
composition [3-4]. In surface coating/ink formulation dispersion is most expensive
component so it is always advantageous to achieve the highest color strength and shade
matching at lowest possible amount of pigment. Correct pigment dispersion technology and
optimum mill base formulation facilitates better color strength, brightness and stability of
final coating formulations. Dispersering and wet grinding techniques for preparation of ready
tints have advantages over the direct paint manufacture in terms of utilization of best
processing technology, faster production and reduced inventory of pigment concentrates.
Current commercial challenge often faced by the surface coating industry is to keep these
pigments in the stable dispersed form with ultimate achievement of colour strength (e.g.
jertness in case of carbon black) The commercially available pigments are dispersed into the
polymeric vehicle/suitable medium by cascading and attrition In these process, high shear
rate homogenization is used to redisperse the pigment agglomerates. However the breaking of
agglomerates requires high energy inputs when high shear rate homogenizers and grinding
process is being used to achieve segregation of particles and dispersion of particles.
Cavitation is one of the ideal options to achieve the segregation of particles and their
stabilized dispersion. Large aggregation of particles are being fragmented into the smaller
particles by use of continuous mechanical shearing action and micro jets, attrition effect and
knife effect by continuous implosion of ultrasound waves. The use of ultrasound power in
grinding and making stable dispersions has numerous of advantages such as it is the most
viable technique for highly energetic grinding materials it does not affect thermal behavior of
materials, requires shortest processing period there is minimum consideration. These
advantages permit use of high intensity ultrasounds for the preparation of variety of
commercial materials in which particle size of major concern such as catalytic materials,
ceramic, pharmaceutical sol, color concentrate. [5-7]. In recent times, the potential use of
ultrasound in leather, textiles, and chemical process industries with the aim to increase the
process efficiency, reduce process time, and improve product quality as an advanced
manufacturing technique are being studied [7] Our earlier studies demonstrated that
ultrasound helps to improve the coloristic properties of coating such as color strength and
purity. In cavitation based dispersion, formation of intense turbulence coupled with strong
liquid circulation currents can enhance mass transfer rates and generate a very fine and stable
dispersion [8] Hence it can be said that physical and chemical effects of ultrasound helps in
the intensification of the dispersion process though micro-jets, micro-mixing and high
shearing as well as extreme adiabatic temperature and pressure conditions. Thus in the
present work, we have proposed the use of ultrasonic irradiation as source of energy to
intensify the process of dispersion which is expected to give beneficial effects via
simultaneous action of shearing and compression.

2. Brief Objectives of the Project

a) To explore the practical issues associated with energy optimization and pigment
dispersibility in ultrasound assisted dispersion of nanopigments in stirred ball mill.
b) To investigate the effects of primary and secondary mechanochemical processes on degree
of dispersion.
c) The experimental outcomes will be analyzed and a vigorous mathematical modeling and
simulation will be performed to optimize the operating conditions for minimum energy
utilization for to achieve maximum tinctorial strength.

3. Methodology
Design and Fabrication of stirred ball mill
A cost effective stirred ball mill will be fabricated for paint dispersion purpose. Effects of
several parameters such as radial distribution of beads, axial distribution of beads as a
function of agitator type and speed on tinctorial strength, purity of colour, colour difference,
gloss, impact resistance, mar resistance, adhesion, hardness, and scratch resistance of film
will be studied by dispersing suitable formulations development in the developed mill.

4. Work done (Phase wise) and Results achieved:

Phase I: a) Literature Survey:
A rigorous literature have been referred (still continues) in the form research papers and
reference books for studying various aspescts of pigment dispersion including methodologies,
mechanism, energy requirements, design of equipments, respective cost of operation and
modeling of dispersion techniques. For generating a bank of information in the form of high
impact referred journal libraries of institutes like IIT Bombay, IIT Kanpur, IISc Bangalore,
UICT Mumbai, NIT Warangal, North Maharashtra University Jalgaon etc have been referred.
List of research papers generated as a part of literature survey have been enclosed (Appendix
I).

b) Design and Fabrication of stirred ball mill.

Amalgamations of ball mill and bead mill is performed in a simple, novel Impeller Assisted
Circulation Mill using circular disc and cross shaped stationary impellers. Mill base
calculations and let down additions were worked out successfully for ball mill, bead mill and
Impeller Assisted Circulation Mill for green glossy paint, yellow chrome glossy paint, white
flat paint, white undercoat paint and white undercoat base yellow tinter and to obtain
formulations that met the requirements of finer dispersion at the lowest material cost and to
verify the feasibility of new design.

The prototype stirred ball mill was designed, fabricated in the institute workshop with
following dimensions.

Sr. No Specification Details

1 Mill diameter 115mm X 116mm (Inside diameter X height)
2 Mill Capacity 1.33 L (suspension)
 3 Motor power 1.5 Hp
4 Motor Speed 400 rpm
5 Electric Supply 230 V, Single Phase, 50 Hz

Stirred Ball Mill

Ultra Sonicator
Phase II: Experimental runs:
Preliminary experiments in batch mode have been completed to study the effect of ultrasound
assisted cavitation on dispersibility of various organic and aqueous based pigment
formulations. Blue and green pigments were selected to make the water and organic solvent
based pigment concentrate in presence of surfactant.
Formulations of Phthalocyanine Blue and Green water based and THF based Dispersions for
Preliminary runs
Formulation-1
Tint base Ingredients Weight (%)
Pigment (Blue/ Green)* 5.156
Surfactant (Tween 80/ SLS/ BYK)* 1.031
Oleic acid* 0.578
Iso propyl alcohol* 10.3
Water based THF 10.3
Water 72.2
Organic solvent based THF 82.5
Total 100
* Common ingredients for both water based and THF based Tints
Operating parameters for Preliminary experimental runs of formulation 1)

Ultrasound Probe
Pigment Surfactant Phase
Size (mm)
6 Tween 80
Blue 10 Sodium Lauryl sulphate
20 BYK-192
Aqueous and Solvent
6 Tween 80
Green 10 Sodium Lauryl sulphate
20 BYK-192
Preliminary experiments on fabricated stirred ball mill have also been carried out with
following formulation
2) Formulation Green Glossy Paint for experimental runs for prototype stirred ball mill
Sr. No. Ingredients Weight in %
1 Phalocyanine Blue 1.0
2 Hansa yellow G 10.0
3 Ferrite yellow 3.5
4 Lond oil alkyd(70% solid) 59.9
5 Mineral turpentine oil 20.6
6 Dipentene 3.0
7 Methyl ethyl ketoxime 0.1
8 Cobalt octoate 0.4
9 Calcium octoate 1.5
Total 100
Solids by volume = 50.3, Sp. gravity = 0.97, %
pigment volume concentration (PVC) = 25.5

The fineness and stability of colloidal dispersion was monitored by AFM analysis, SEM
analysis and particle size distribution while colour matching spectral analysis (K/S analysis)
was undertaken to determine the variation in colour strength.
Color strength analysis
A) Formulation-1
Water Based
Color Probe 1 (6mm) Probe (10mm) Probe(20mm)
WT-
WT-6 WS-6 WB-6 WS-10 WB-10 WT-20 WS-20 WB-20
10
Blue 65.41 68.88 75.25 9.24 69.08 67.06 50.22 71.67 63.37
Green 82.77 87.02 91.34 35.02 49.17 9.007 55.05 99.86 68.71
Solvent Based
Color Probe 1 (6mm) Probe (10mm) Probe(20mm)
ST-6 SS-6 SB-6 ST-10 SS-10 SB-10 ST-20 SS-20 SB-20
Blue 93.02 100 93.37 76.77 82.75 73.44 66.80 69.21 71.82
Green 78.67 88.34 56.09 61.9 100 20.10 25.73 57.98 77.72

B) Formulation 2

AFM analysis for formulation 1

SEM analysis for Formulation 2

(2 hrs) (4 hrs)
 (6hrs)

Particle Size Distribution results Formulation 1:

Average
Particle size Particle size Average particle size
Pigment particle size in
distribution distribution in nm
nm
Probe tip (mm) 6 20
Blue Pigment 78-825 451 68-531 299

Particle size distribution of blue pigment (organic) when a) 6 mm probe tip b) 20 mm probe
tip was used and particle size distribution of Green pigment (organic) when c) 6 mm probe
tip and d) 20 mm probe tip was used in water solvent.
Comparison of energy required achieving complete dispersion by high speed dispersion mill
and high intensity ultrasound was investigated. Correlation was established with dispersion
quality parameters and energy consumption, quantity of surfactant.
Following achievements from work carried out in the project:
a) Patent: 01 patent filled as detailed below
Title: Design of Impeller assisted circulation milling for finer dispersion
Application No.: 1844/MUM/2012
Ref. No.: E-11/138/2012-MUM
Date of filing: 27/06/2012
b) Conferences
Sr. Name of Internationa Date and Venue Title of Paper/Poster
No. Conference l/National presented
1. 9th International International 7-9 Dec. 2011 Surfactant assisted ultrasound
Symposium on Banglore, India dispersion of phthalocyanine
Surface Protective pigments in water borne and
Coatings (SSPC solvent thinnable systems:
2011 India) Modeling and Simulation
studies
3. Nanomaterials National 18 Feb. 2012 “Surfactant mediated synthesis
Industrial Polymer SOCS and UDCT, and ultrasound dispersion of
and Eco-friendly North Maharashtra nano Iron Oxide Pigment”
Coatings Prespective University,
and Challenges Jalgaon.
(NIPEC-2012)
4. 8th Coating Science International 25 - 29 June 2012 “Mathematical modeling of
International 2012 Noordwijck, The microbead and high speed
Netherlands dispersion and evaluation of
dispersion stabilization
mechanism”
6. 10th International International Feb. 15-16, 2013 “Phase selective synthesis of
Symposium On Mumbai bismuth vanadate (BiVO4)
Surface Protective nanopigment using surfactant
Coatings, SSPC assisted impinging solution
India 2013 (SSPC- spray process and their
2013), (2 nd Best application as high performance
poster paper pigment in paint”
awarded).
7. Nano India 2013 National 19-20, February “Polymorph selective synthesis
2013, of CaCO3 nanoparticles using
Thiruvananthapura impinging solution spray
m, India process and their utilization for
preparation of PBSA/ CaCO3
 Latex Composites”

8. 5th Asian Conference International Department of “Synthesis of copper

on Colloid and Chemistry, phthalocyanine blue
Interface Science University of North nanopigment comparative
[ACCIS-2013] Bengal, Darjeeling, evaluation of fusion, solvent and
West Bengal, microwave technique”
India, 20-23
November 2013.

Summary of the findings:

Amalgamations of ball mill and bead mill is performed in a simple, novel Impeller Assisted
Circulation Mill using circular disc and cross shaped stationary impellers. Mill base
calculations and let down additions were worked out successfully for finer dispersion of
green glossy paint, yellow chrome glossy paint, white flat paint, white undercoat paint and
white undercoat base yellow tinter to verify the feasibility of new design. Comparison of
energy required achieving complete dispersion by newly fabricated ball mill and high
intensity ultrasound was investigated.
Correlation was established with dispersion quality parameters and energy consumption,
quantity of surfactant.
Contribution to the society:
Dispersion of pigment concentrates is an important processing step in the formulations of
paints and coatings. Current commercial challenge often faced by the surface coating industry
is to keep these pigments in the stable dispersed form with ultimate achievement of colour
strength. We demonstrated that newly fabricated ball mill and ultrasound helps to improve
the coloristic properties of coating such as color strength and purity and will be beneficial for
optimizing the operating conditions for minimum energy utilization for to achieve maximum
tinctorial strength for many paint surface coating industries.

Ph.D. enrolled/produced out of the project:

Yes, Co-investigator Mr. Nilesh P. Badgujar and Project Fellow Mr. Yogesh E. Bhoge
have enrolled for Ph. D.
Details are as follow:
Name of Enrolled Mr. Nilesh P. Badgujar Mr. Yogesh Eknath Bhoge
Candidate
Post Co-Investigator Project Fellow
University North Maharashtra university, North Maharashtra university, Jalgaon
 Jalgaon (M. S.) India (M. S.) India
Faculty Engineering and Technology Science
Subject Chemical Engineering Chemistry
Title Physicochemical “Synthesis and crystal design of high
characterization, process performance pigments for development
Engineering and of special effect coatings”
Mathematical Modelling of
Pigmented Dispersion for
Utilization in Formulation of
caotings
Registration No. NMU/11/Ph. D/Chem. NMU/11/Ph.D./Chem/277/2012, Dated:
Engg./28/2011, Dated 20/01/2012
23/02/2011

No. of publications out of the project:

Published: 02, Communicated: 00 (Reprints are enclosed)

1. N P Badgujar, Y E Bhoge, T D Deshpande, Bharat Apparao Bhanvase, Parag

Gogate, Shirish H Sonawane, Ravindra D Kulkarni, “Ultrasound assisted organic
pigment dispersion: advantages of ultrasound method over conventional method”,
Pigment and Resin Technology, Vol. 44, Issue 4, pp. 214-223, (2015) [IF: 0.79].

2. Y. E. Bhoge, V. J. Patil, T. D. Deshpande, U. D. Patil and R. D. Kulkarni, “Synthesis

of Mica Doped Calcium Carbonate Filler for Partial Replacement of TiO2 in
Decorative Paint”, International Journal of Engineering Trends and Technology, pp.
279-282, (2016) [IF: 1.79]
 Pigment & Resin Technology
Ultrasound assisted organic pigment dispersion: advantages of ultrasound method over conventional method
N.P. Badgujar Y.E. Bhoge T.D. Deshpande B.A. Bhanvase P.R. Gogate S.H. Sonawane R.D. Kulkarni
Article information:
To cite this document:
N.P. Badgujar Y.E. Bhoge T.D. Deshpande B.A. Bhanvase P.R. Gogate S.H. Sonawane R.D. Kulkarni , (2015),"Ultrasound
assisted organic pigment dispersion: advantages of ultrasound method over conventional method", Pigment & Resin
Technology, Vol. 44 Iss 4 pp. 214 - 223
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 Ultrasound assisted organic pigment
dispersion: advantages of ultrasound method
over conventional method
N.P. Badgujar, Y.E. Bhoge and T.D. Deshpande
Institute of Chemical Technology, North Maharashtra University Jalgaon, India
B.A. Bhanvase
Department of Chemical Engineering, Laxminarayan Institute of Technology, Nagpur, India
P.R. Gogate
Department of Chemical Engineering, Institute of Chemical Technology, Mumbai, India
S.H. Sonawane
Department of Chemical Engineering, National Institute of Technology, Warangal, India, and
Downloaded by Indian Institute of Technology at Kanpur At 22:59 12 December 2016 (PT)

R.D. Kulkarni
Institute of Chemical Technology, North Maharashtra University Jalgaon, India

Abstract
Purpose – The present work aims to deal with ultrasound-assisted organic pigment (phthalocyanine blue and green) dispersion and its comparison
with the conventional approach.
Design/methodology/approach – Ultrasound is expected to give beneficial results based on the strong shear forces generated by cavitational
effects. The dispersion quality for preparation using an ultrasound-based method has been compared with dispersion obtained using high-speed
dispersion mill. Effects of different operating parameters such as probe diameter and use of surfactants on the physical properties of dispersion and
the colour strength have been investigated. Calculations for the energy requirement for two approaches have also been presented.
Findings – The use of sodium dodecyl sulphate and Tween 80 surfactants shows better performance in terms of the colour properties of dispersion
prepared in water and organic solvent, respectively. Ultrasound gives better dispersion quality as compared to the conventional approach.
Originality/value – The present work presents a new approach of ultrasound-assisted dispersion of phthalocyanine blue and green pigments.
Understanding into the effect of surfactants and type of solvent also presents new important design-related information.
Keywords Dispersions, Ultrasonic frequencies, Surfactants
Paper type Research paper

Introduction including metal, plastic, wood and glass surfaces. The current
commercial challenge often faced by the surface coating industry
Dispersion of pigment concentrates is an important processing
is stability of the pigment dispersion. The conventional approach
step in the formulations of paints and coatings (Smith, 2002). A
for dispersion of commercially available pigments into suitable
narrow range of particle-size distribution in the final product
medium is based on the use of high-speed homogeniser. In this
achieved due to the efficient pigment dispersion process
approach, high shear mixer is used to redisperse the pigment
facilitates improved colour strength, brightness and stability
agglomerates but the use of high shear homogenising mixer
(Wennerstrum et al., 2002). Superior dispersion of
requires higher energy input to break tightly bound aggregates
nanomaterials can be achieved using different surfactants
(Suslick et al., 1996; Raman et al., 2011; Huang and Terentjev,
(Vaisman et al., 2006; Zheng et al., 2003; Hwang et al., 2008)
2012; Perez-Maqueda et al., 2005). To break the aggregates of
and a range of aqueous/organic solvents have also been explored
the particles, the supplied energy must be greater than the
as dispersion media (Giordani et al., 2006; Cheng et al., 2008;
binding energy of the aggregates. An alternative approach for
Bergin et al., 2009). Water- and organic solvent-based dispersion
obtaining a uniform dispersion can be based on the use of
can be used in coatings that can be applied to most substrates,
sonochemical reactors, which work on the principle of cavitation.
Cavitation is caused by passing high-frequency sound waves
above 20 kHz through liquid media. When ultrasound passes
The current issue and full text archive of this journal is available on
Emerald Insight at: www.emeraldinsight.com/0369-9420.htm
The authors acknowledge the financial assistance of University Grants
Commission (UGC), New Delhi under the scheme of Major Research
Project [F. No. 40-11/2011(SR)].
Pigment & Resin Technology
44/4 (2015) 214 –223 Received 11 April 2014
© Emerald Group Publishing Limited [ISSN 0369-9420] Revised 4 January 2015
[DOI 10.1108/PRT-04-2014-0033] Accepted 4 January 2015

214
 Ultrasound-assisted organic pigment dispersion Pigment & Resin Technology
N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

through the liquid media, molecules are pulled apart in the dispersion of organic pigment evaluating the effect of
rarefaction cycle to create cavities which then pass through probe diameter and addition of different surfactants. Two
different stages of growth and size oscillations before commercially important organic pigments (phthalocyanine
collapsing violently generating various physical and chemical blue and green) have been considered for the dispersion study
effects (Bhanvase et al., 2011, 2012a, 2012b; Prasad et al., in different organic solvents. Energy consumption analysis has
2010; Pinjari and Pandit, 2010, 2011). The extreme transient also been attempted to establish the efficacy as compared to
conditions generated in the vicinity and within the collapsing the conventional approach.
cavitational bubbles can bring about the size reduction of the
material to nanoscale (Patel et al., 2013; Deosarkar et al., Experimental
2013). The strong shear force generated during the cavity
Materials
collapse can also effectively disperse the pigments, and the
Pigments such as phthalocyanine blue (CuC32H16N8, specific
effects are dependent on several factors such as nature of the
gravity: 1.6-1.8, oil absorption value of 43 per cent) and
solvent including the physicochemical properties, number of
phthalocyanine green (C32H16ClN8, specific gravity:
cavitation events, operating temperature and pressure, as well
1.4-1.45, oil absorption value of 36 ⫾ 6 per cent) were
as the ultrasound parameters such as intensity, frequency and
procured from Sudarshan Chemicals, Pune. Tween 80
irradiation time. The use of ultrasound in the formulation of
(polyoxyethylene sorbitan monooleate, density of 1.07 g/cm3
Downloaded by Indian Institute of Technology at Kanpur At 22:59 12 December 2016 (PT)

stable dispersion has many advantages, and this approach can

at 25°C) was procured from Loba Chemie, Mumbai. Oleic
be a viable technique for the preparation of small, uniform-size
acid (analytical grade, density 0.895 g/cm3) was procured
particles of colloidal materials. Further, the use of ultrasound from Merck Specialties Pvt. Ltd., Mumbai. Sodium dodecyl
does not alter the thermal behaviour of materials and sulphate (SDS, C12H25SO4Na, density of 1.01 g/cm3) was
dispersion can be achieved in lower processing time (Raman procured from S. D. Fine Chemicals Pvt. Ltd., Mumbai.
et al., 2011; Huang and Terentjev, 2012; Perez-Maqueda Distilled water was used as a medium for the preparation of
et al., 2005; Bhanvase et al., 2011, 2012a, 2012b; Patel et al., water-based dispersion. BYK 192 acrylic polymeric surfactant
2013; Deosarkar et al., 2013; Suslick et al., 1987; Raman and was obtained as a gift sample from BYK Chemie (pH 5-9,
Abbas, 2008; Patil and Pandit, 2007). density of 1.05 g/cm3 at 20°C). Organic solvents such
There have been some earlier reports related to the use of as isopropyl alcohol (density of 0.786 g/cm3) and
ultrasound for pigment dispersion, and recently, Hielscher tetrahydrofuran (density of 0.889 g/cm3) were obtained from
(2013) has provided a good overview of the applications of S.D. Fine Chemicals Pvt. Ltd., Mumbai, and Merck
ultrasound in the area of paints and coatings. Some of the Specialties Pvt. Ltd., Mumbai, respectively. All chemicals
earlier works related to use of sonication for dispersion and were used as received from the supplier.
stabilisation of pigments include the work of Cheng et al.
(2010a) and Bergin et al. (2008). The quality of dispersion is Pigment dispersion using conventional high-speed
dependent on the sonication conditions including sonicator homogeniser and ultrasound
types, sonication times (generally reported range is 2 to 30 The dispersion of pigment in organic solvents- and water-
min) and probe diameter. In addition, the solvent properties based systems has been investigated using an ultrasound-
also affect the dispersion process, and the effects have been assisted approach based on the use of ultrasonic horn
generally analysed on the basis of solubility parameters such as (diameters 6, 10 and 20 mm) operating at a constant
Hildebrandt or Hansen parameters (Cheng et al., 2008; frequency of 22 kHz and the rated output power of ultrasonic
Bergin et al., 2008; Cheng et al., 2010a; Cheng et al., 2010b; horn was 750 W (Crometech Model, Taiwan). The actual
Usrey et al., 2009; Detriche et al., 2008) or surface energy power input could be controlled by varying the amplitude. In
(Bergin et al., 2008). Scale-up of ultrasonic reactors has been the present work, an ultrasonic horn was operated at 50 per
a problem over the years, but the recent advances into new cent amplitude giving supplied power of 375 W. Experiments
efficient designs such as flow cells, designs based on were carried out to understand the effect of probe diameter on
longitudinal horns or multiple transducers and continuous the extent of deagglomeration and the colour strength. The
processing have made some applications possible at effect of probe diameter was investigated using different
commercial-scale installations (Kumar et al., 2007; Gogate diameters as 6, 10 and 20 mm diameter and the treatment
et al., 2003, 2011; Gogate, 2008). Englert et al. (2012) time was fixed at 30 min. For establishing the efficacy of the
reported the scaling up of a process for achieving dispersion of ultrasound-based approach, conventional approach was also
nanoparticles in epoxy resin using ultrasound-assisted used for preparation of water- and organic solvent-based
continuous flow operation. dispersions using a high-speed dispersion mill (0.125 HP,
An analysis of the literature reveals that there has not been 8,000 RPM 230 V, Make REMI Mumbai, India).
much work regarding the establishment of the dependency of
quality of dispersion on the probe diameter which plays an Formulation of blue and green pigment dispersions
important role in deciding the physical effects of cavitation. The formulations of phthalocyanine blue and green (water-
The effect of the presence of surfactants which can alter and organic solvents-based dispersions) were prepared as per
the stability of the prepared dispersions in combination of the compositions reported in Table I. Three different
ultrasound has not been studied in details. A comparison of surfactants, SDS, Tween 80 and BYK 192, were selected for
the energy requirements for the ultrasound-assisted approach the water- and organic solvent-based dispersion (Usrey et al.,
and conventional milling processes is also lacking. The present 2009). Based on hydrophilic–lipophilic balance values, the
work deals with the use of ultrasonic irradiation for the selection of surfactant type and quantity was decided. SDS

215
 Ultrasound-assisted organic pigment dispersion Pigment & Resin Technology
N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

Table I Formulations of phthalocyanine blue and green water-based and THF-based dispersions
Serial no. Ingredients Waterborne pigment concentrate Organic solvent-based pigment concentrate
ⴱ
1 Pigment (blue/green) 5.2 5.2
2 Surfactant (Tween-80/sodium 1.0 1.0
lauryl sulphate/BYK-192)ⴱ
3 Oleic acidⴱ 0.6 0.6
4 Isopropyl alcoholⴱ 10.3 10.3
5 Tetrahydrofuron 10.33ⴱⴱ 82.5
6 Water 72.2 –
Notes: ⴱ Common ingredients for both water-based and organic solvent-based pigment concentrate; ⴱⴱ
small quantity of THF is used in water-based
pigment concentrate as pigment is hydrophobic

Figure 1 Microscopic images at 40 ⫻ magnification of the

surfactant was used mainly in the water-based formulation,
ultrasound-assisted dispersed blue pigment in the water-based
while Tween 80 was used mainly in the organic-based
system using
formulations. Other ingredients such as oleic acid, isopropyl
Downloaded by Indian Institute of Technology at Kanpur At 22:59 12 December 2016 (PT)

alcohol were common ingredients in both the water- and

organic solvent-based system. At room temperature, organic
pigments such as phthalocyanine blue and phthalocyanine
green (5 weight% loading) were dispersed in the presence of
different surfactants (Tween 80/SDS/BYK) in a 250-ml
beaker. In a typical formulation, 1 g surfactant (Tween 80/
SDS/BYK), 0.578 g oleic acid, 10.3 g of isopropyl alcohol,
10.3 g of tetrahydrofuran (THF) and 72.2 ml of water was
mixed in the case of water-based system; 82.5 gm of THF was
added instead of a mixture of THF (10.3 g) and water (72.2
ml) for the case of organic solvent-based dispersion (all the
other components were mixed in same ratio).

Characterisation
Atomic force microscopy (AFM) measurements were performed
using an AFM Explorer microscope (ThermoMicroscopes,
USA) at room temperature, in a non-contact mode with Si
cantilevers of a 1,650-00 type (ThermoMicroscopes) with a
nominal tip radius of 10 nm and resonant frequency of about 220
kHz. Colour strength (K/S) of the pigment was measured using
the standard reset method for colour and strength of the
pigments (ASTM D387-00) which measures the K/S values
using a reflectance spectrophotometer based on the Kubelka
Munk equation. The size distribution and average particle size of
phthalocyanine blue pigment were obtained using an optical
microscope (Olympus CX21). Particle-size distribution analysis ultrasound-assisted dispersion using 20-mm probe gives the
of phthalocyanine green pigments was carried out by Photon best colour strength due to finer dispersion as compared to the
Correlation Spectroscopy (PCS, 3,000 HAS, analyser, Malvern) 10-mm-diameter probe in both water- and organic solvent-
with images being acquired at a magnification of 40 ⫻. based system. An image of colour shade prepared by the
20-mm probe shows lesser agglomeration of the particles,
while images of colour shade prepared by the 10-mm probe
Results and discussion
show the presence of coarser particles. The above results
Comparison of microscopic images of dispersion clearly indicate that the 20-mm probe is more efficient in
prepared using high-speed dispersion mill and breaking the agglomeration of pigment particles. Generation
ultrasound-based method of fine dispersion in the presence of ultrasound is attributed to
Pigment dispersions prepared using high-speed dispersion the physical effects of cavitation, namely, intense micro-scale
mill as the conventional approach were compared with those turbulence and acoustic streaming (Vichare et al., 2001;
prepared using ultrasound (10- and 20-mm– diameter probe) Tuziuti et al., 2005; Gogate, 2008; Chen et al., 2010;
based on the microscopic colour images of phthalocyanine Moholkar et al., 2000). Use of the high-speed dispersion mill
blue pigment dispersion as shown in Figure 1. Comparison of does not provide intense mixing at micro scale and hence it
the images depicted in Figure 1(a-f) reveals that the high- results into agglomeration of pigments. Also, in the case of the
speed dispersion mill shows maximum agglomeration as 20-mm-diameter probe, increased extent of cavitation and
compared to the ultrasound-assisted dispersion for both 10- liquid circulation velocity (Vichare et al., 2001) gives higher
and 20-mm-diameter probe. It is also observed that breakage of agglomerates as compared to the 10-mm probe,

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N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

resulting in fine dispersion. It is also established that higher representation), which can be attributed to the fact that the
energy delivery through a smaller area of the tip (in the case of wave intensity produced by these probes with 6- and 10-mm
10-mm probe) gives some fraction of particles with smaller diameter is near about similar. From Figure 2(a), it is
size and remaining particles lie in the large particle size range observed that the 6-mm probe shows the particle-size
giving uneven dispersion of particles. In the case of the 20-mm distribution in the range of 78-825 nm with average particle
probe, the particles are obtained in narrow range as compared size as 451 nm, while the blue pigment dispersion prepared
to the 10-mm probe because of increased liquid circulation using the 20-mm probe shows narrow particle-size
velocity (Vichare et al., 2001) giving uniform and finer distribution over the range of 68-531 nm with average
dispersion of pigment. The effect of probe diameter should particle size as 299 nm (Figure 2(b)). Particle-size analysis
not be generalized, as any continuous increase in probe clearly indicates that the narrow range of distribution is
diameter may cause a decrease in the efficiency as a result of obtained using the 20-mm probe. It is attributed to
increasing probe weight and overloading of piezoelectric and increased cavitational activity and hence increased liquid
electric power source. Also, with an increase in the probe circulation velocity due to the increase in probe diameter
diameter after a certain value, it is expected that ultrasonic from 6 to 20 mm (Vichare et al., 2001) resulting in uniform
wave reflection in the direction perpendicular to the probe axis and fine dispersion. Due to higher active cavitational
increases and a decrease in the extent of cavitation occurs. volume, it is expected that there will be higher breakage of
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Due to these reasons, it is recommended that the probe agglomerates in the case of the 20-mm probe as compared
diameter should be less than a quarter of the probe length to the 6-mm probe, which results in a narrower particle-size
(Mcculloch, 2008). distribution. It should be noted that larger diameter till an
optimum value (Mcculloch, 2008) will be more preferred
Particle-size analysis of organic pigment dispersion: where narrow overall size distribution is required with lower
effect of the probe diameter average size of the dispersion.
Figure 2 represents the particle-size distribution of
phthalocyanine blue pigment obtained from the experiments
AFM analysis of organic pigment dispersion: effect of
based on the use of 6- and 20-mm probe tip in the case of the
probe diameter and surfactant
ultrasound-assisted approach with SDS as a surfactant in the
Figure 3(a-d) shows the representative AFM images of the
water-based system. Further, it was also observed that 6- and
four best batches obtained in the present work for the
10-mm-diameter probe gives comparable results (data for 10
comparison purpose. Figure 3(a) represents the AFM image
mm not shown to avoid repetition and give clarity in
of blue pigment dispersion prepared using Tween 80
Figure 2 Particle-size distribution of blue pigment (organic) along surfactant using 20-mm ultrasonic probe for the organic
with SDS surfactant in the water-based system solvent-based system. Figure 3(b) represents the AFM image
of water-based blue pigment dispersion using an SDS
surfactant in the presence of the 20-mm ultrasonic probe.
Figure 3(c) shows an AFM image of organic solvent-based
blue pigment dispersion using BYK-192 surfactant using
20-mm ultrasonic probe. Figure 3(d) shows the three-
dimensional image of the water-based blue pigment dispersion
obtained using the 20-mm ultrasonic probe. From Figure 3, it
is observed that the dispersion prepared by the 20-mm probe
in the aqueous system in the presence of SDS surfactant shows
the best dispersion characteristics as depicted in Figure 3(b
and d). On the other hand, Figure 3(c) shows the least
dispersion when blue pigment dispersion was prepared in the
presence BYK surfactant using organic solvent-based system
with the 20-mm probe. The use of the 20-mm probe size and
SDS surfactant showed better dispersion as compared to other
surfactants. The exact order of effective dispersion in these
systems (dispersion of blue pigment prepared by ultrasound
assisted approach using the 20-mm probe) is as follows:
water-based system in the presence of SDS surfactant ⬎
organic solvent-based system in the presence of Tween 80
surfactant ⬎ water-based system in the presence of BYK-192
surfactant. It is also established that dispersion prepared using
the 20-mm probe shows a more regular pattern of distribution
of particles because of increased cavitational activity (Vichare
et al., 2001) for the case of larger diameter of the probe as
reported in the Figure 3(b). It is also found that the use of
SDS surfactant showed uniform and fine particles in
dispersion prepared using the 20-mm probe in the water-
based system (Figure 3(b)). It is also observed that Tween 80

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Figure 3 (a) Two-dimensional AFM image of blue pigment dispersion prepared in Tween 80 surfactant organic solvent-based system using the 20-mm probe;
(b) Two-dimensional AFM image water-based blue pigment dispersion using SDS surfactant and the 20-mm-diameter probe; (c) Two-dimensional image of green pigment
dispersion prepared by BYK surfactant – organic solvent based-system under the 20-mm-diameter probe; (d) Three-dimensional image of the water-based blue pigment
dispersion using SDS surfactant and the 20-mm-diameterprobe
N.P. Badgujar et al.
Ultrasound-assisted organic pigment dispersion

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 Ultrasound-assisted organic pigment dispersion Pigment & Resin Technology
N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

surfactant shows good dispersion of organic pigments with the presence of surfactant. Due to increasing intensity of
use of the 20-mm probe in the organic solvent-based system ultrasound, there is no effect on the surface charge, but there
with some degree of agglomeration. is a reduction in the pigment particle size due to the effects of
cavitation. The reduction in the size is also dependent on the
Effect of the probe diameter and surfactant type on addition of suitable surfactant and the combined effect is
the viscosities of dispersion helpful for the uniform distribution of the pigment particles in
For processing stable colloidal dispersions, two main features the suspension. The role of surfactants is attributed to the
of surfactants, namely, adsorption at interface and self- pigment wetting that is achieved when suitable surfactants and
accumulation into supramolecular structures, are very solvents adhere to exposed pigment surfaces. Surfactants
important. The adsorption of surfactants on the inorganic and sustain pigment particle separation by maintaining a
organic surfaces generally depends on the chemical minimum safe distance between two pigment particles of
characteristics of particles, surfactant molecules and solvent. about approximately 5 nm. If the distance between pigment
The effect of the probe diameter and surfactant type on the particles is less than the minimum safe distance, attractive
viscosities of dispersion prepared in organic solvent and water forces will bring particles together, forming flocculates.
has been depicted in Table II. It is found that the dispersion of Flocculation leads to noticeable changes in the pigment
organic pigments prepared in the organic solvent-based properties such as colour strength, gloss and viscosity. Thus,
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system shows higher viscosity (ranging from 46.5 to 479 cps) the overall enhancement in the colour strength is attributed
in the presence of different types of surfactants and to the combined effect of surfactant and ultrasonic irradiation.
ultrasound. It is attributed to the higher viscosity of organic The variations in colour strength of prepared dispersion using
solvent compared with water, which is further enhanced by the different diameter probes and surfactant type are represented
addition of pigments in the organic solvent. Water-based in Figure 4(a and b). As evident from the Figure 4(a and b),
dispersion shows the viscosity ranging from 0.74 to 70 cps in it is found that water-based dispersion show highest colour
the presence of different types of surfactants and ultrasound strength in the case of dispersion obtained in the presence of
which is less than the organic solvent-based pigment SDS surfactant. It is also found that an increase in the
dispersion. diameter of the probe does not show any appreciable change
SDS surfactant was found to be effective in combination in the colour strength, when SDS surfactant was used in the
with ultrasound in the case of the 10-mm probe in the water-based system. On the contrary, BYK-192 shows clear
water-based system giving the minimum viscosity as 0.74 cps. effect of the diameter of the probe on colour strength. It is
It is attributed to the formation of more homogeneous found that an increase in the diameter of the probe results in
pigment dispersion in the aqueous medium. In the case of a reduction in the colour strength in the presence of BYK-192
organic solvent-based pigment dispersions, with an increase in surfactant. The observed results can be attributed to a
the ultrasound probe diameter, the viscosity values are found reduction in the coverage of particles by BYK-192 surfactant
to decrease, indicating more homogeneous pigment due to an increase in the probe size resulting in reduction in
dispersion. In the case of Tween 80 and SDS surfactants in the final colour strength [Figure 4(a)]. In the case of organic
the organic solvent-based system, the viscosities were found to solvent-based system [Figure 4(b)], use of higher probe
be reduced from 375.0 to 114.8 and 416.3 to 73.66 cps, diameter during the dispersion results in a decrease in the
respectively. The observed decrease in the viscosity can again colour strength. This might be due to degradation of organic
be attributed to higher cavitational activity (Vichare et al., compounds in the presence of larger size probes which gives
2001) at larger size of the ultrasound probe. For the BYK 192 higher cavitational intensity. It is also interesting to note that,
and Tween 80 surfactants, the viscosities of organic all surfactants show better colour strength in the organic
solvent-based dispersion are 46.50 and 114.8 cps at 20-mm solvent-based system. Tween 80 and BYK surfactant shows
ultrasound probe diameter, respectively, which can be almost the same performance.
attributed to the formation of more homogeneous pigment
dispersion using BYK 192 surfactant as compared to Tween Prediction of deagglomeration using probability
80 surfactant. analysis
Paint properties such as colour strength and viscosity changes
Variation in the colour strength significantly with the degree of deagglomeration. Therefore,
For the enhancement in the colour strength, uniform the colour strength (K/S) can be considered as representative
distribution of pigment particles is required, which is of the extent of dispersion of the agglomerates under active
dependent on the ultrasound probe diameter, as well as the dispersion volume (as per first-order kinetic model). The

Table II Effect of surfactant and the diameter of the probe on the viscosities of the pigment concentrate
Probe (6 mm) Probe (10 mm) Probe (20 mm)
Colour Tween 80 SDS BYK-192 Tween 80 SDS BYK-192 Tween 80 SDS BYK-192
Viscosity values (cps) water-based
Blue 9.6 7.06 1.302 4.09 0.74 9.11 69.94 63.43 2.79

Viscosity values (cps) organic solvent-based

Blue 375.0 416.8 479.3 129.3 171.9 145.3 114.8 73.66 46.50

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N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

Figure 4 Effect of the surfactant type, ultrasound and diameter of Figure 5 Probability predictions of ultrasound and high-speed
the probe on colour strength of green pigment disperser vs time in minute
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green pigment dispersion with the use of BYK surfactant

shows the lowest extent of deagglomeration, while organic
solvent-based blue pigment dispersion using Tween 80
surfactant under 6-mm-diameter probe resulted in maximum
colour strength values (K/S) obtained for different dispersions dispersion.
using different diameter of probe for each surfactant have been
reported in Table III. The morphology of pigment dispersion Comparison of the energy efficiency of the ultrasound-
for four best batches has been depicted in Figures 5(a and b). assisted method and high-speed dispersion mill
It is observed that the degree of dispersion is the maximum in The energy required for the pigment dispersion using the
the case of blue pigment dispersion, prepared using Tween 80 ultrasound-assisted method and high-speed dispersion mill
surfactant and ultrasound (6-mm-diameter probe) for the has been estimated as per the procedure described in
organic solvent-based system, showing a K/S value of 2.395. Appendix (Detriche et al., 2008; Usrey et al., 2009; Cheng
Organic solvent-based green pigment dispersion prepared et al., 2010a). The energy utilized for the pigment dispersion
with the use of BYK surfactant under the 20-mm probe shows has been expressed as the total energy required (kJ) per unit
the least dispersion with a K/S value of 1.916 and approximate weight of the material (g) present in the system. Both the
average particle size of 4.5 ␮m. The probability of dispersion high-speed dispersion mill and ultrasound-assisted process
for the various formulations shows that organic solvent-based require 30 minutes for the pigment dispersion. The total

Table III K/S values and colour strength (%) for different batches at t ⫽ 30 min
Probe (6 mm) Probe (10 mm) Probe (20 mm)
Colour Tween-80 SDS BYK-192 Tween-80 SDS BYK-192 Tween-80 SDS BYK-192
Water-based
Blue 1.533 1.390 1.065 0.499 0.907 1.008 0.791 0.470 0.881
(94.96) (100) (104.88) (13.42) (100.28) (97.35) (72.91) (104.04) (91.99)
Green 0.518 0.421 0.127 0.447 0.322 0.081 0.339 0.627 0.641
(82.77) (87.02) (91.34) (35.02) (49.17) (9.007) (55.05) (99.86) (68.71)

Organic solvent-based
Blue 2.395 1.253 1.916 1.183 0.913 1.341 1.123 0.784 0.806
(135.04) (145.16) (135.55) (111.45) (120.13) (106.61) (96.98) (100.47) (104.26)
Green 0.477 0.525 0.362 0.434 0.737 0.166 0.172 0.368 0.902
(78.67) (88.34) (56.09) (61.9) (100) (20.10) (25.73) (57.98) (77.72)

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N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

energy required per unit mass of formulations in the Bhanvase, B.A., Pinjari, D.V., Sonawane, S.H., Gogate, P.R.
ultrasound-assisted system with 6-, 10- and 20-mm probes is and Pandit, A.B. (2012a), “Analysis of semibatch emulsion
8.80, 6.75 and 2.20 (kJ/g), respectively, while the energy polymerization: role of ultrasound and initiator”, Ultrasonics
required for high-speed dispersion mill is 15.21 kJ/g. Thus, it Sonochemistry, Vol. 19 No. 1, pp. 97-103.
is clearly established that ultrasound-assisted pigment Chen, Q., Boothroyd, C., Soutar, A.M. and Zeng, X.T.
dispersion is an energy-efficient method in comparison to the (2010), “Sol– gel nanocoating on commercial TiO2
high-speed dispersion mill. Energy saving of 13.01 kJ/g was nanopowder using ultrasound”, The Journal of Sol-Gel
observed when 20-mm-diameter probe is used for pigment Science and Technology (JSST), Vol. 53 No. 1, pp. 115-120.
dispersion. Cheng, Q., Debnath, S., Gregan, E. and Byrne, H. (2010a),
“Ultrasound-assisted SWNTs dispersion: effects of
Conclusions sonication parameters and solvent properties”, Journal of
Physical Chemistry C, Vol. 114 No. 19, pp. 8821-8827.
The effective application of ultrasound in the dispersion of
organic pigments (phthalocyanine blue and green) in water Cheng, Q.H., Debnath, S., Gregan, E. and Byrne, H.J.
and organic solvents has been demonstrated with beneficial (2008), “Effect of solvent solubility parameters on the
results. Particle-size analysis clearly indicates that small dispersion of single-walled carbon nanotubes”, Journal of
particle size is obtained when ultrasound with a probe Physical Chemistry C, Vol. 112 No. 51, pp. 20154-20158.
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diameter of 20 mm is used in the presence of SDS surfactant Cheng, Q., Debnath, S., O’Neill, L., Hedderman, T.G.,
during the water-based dispersion and particle-size Gregan, E. and Byrne, H.J. (2010b), “Systematic study of
distribution becomes narrower when the larger-diameter the dispersion of SWNTs in organic solvents”, Journal of
ultrasound probe (20 mm) was used with reduced average Physical Chemistry C, Vol. 114 No. 11, pp. 4857-4863.
particle size. The order of effectiveness of the dispersion in Deosarkar, M.P., Pawar, S.M., Sonawane, S.H. and
these systems is as follows: blue pigment dispersion prepared Bhanvase, B.A. (2013), “Process intensification of uniform
by an ultrasound-assisted process using a 20-mm probe in an loading of SnO2 nanoparticles on graphene oxide
organic solvent-based system in the presence of Tween 80 nanosheets using a novel ultrasound assisted in-situ
surfactant ⬎ blue pigment dispersion prepared using chemical precipitation method”, Chemical Engineering
20-mmdiameter probe in a water-based system in the presence Process: Process Intensification, Vol. 70 No. 1, pp. 48-54.
of SDS surfactant ⬎ green pigment dispersion prepared using Detriche, S., Zorzini, G., Colomer, J.F., Fonseca, A. and
a 20-mm probe in an organic solvent-based system in the Nagy, J.B. (2008), “Application of the Hansen solubility
presence of the BYK surfactant. The use of an organic solvent parameters theory to carbon nanotubes”, Journal of
and an increase in the probe diameter resulted in a decrease in Nanoscience and Nanotechnology, Vol. 8 No. 11,
the colour strength. It is also interesting to know that all pp. 6082-6092.
surfactants show better colour strength in the organic Englert, M., Bittmann, B., Haupert, F. and Schlarb, A.K.
solvent-based system. Overall, the present work has reported (2012), “Scaling-up of the dispersion process of nanoparticle-
beneficial results in terms of synthesis of uniform and fine agglomerates in epoxy resin with an innovative continuous
dispersion using a combination of ultrasound and surfactant. ultrasonic flow-through-cell dispersion system”, Polymer
Engineering and Science, Vol. 52 No. 1, pp. 102-107.
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ultrasound on inorganic solids”, Ultrasonics, Vol. 25 No. 1, Actual energy delivered by the 20-mm horn during
pp. 56-59. sonication ⫽ energy delivery rate ⫻ total dispersion time ⫻
Suslick, K.S., Hyeon, T. and Fang, M. (1996), efficiency of horn ⫽ 10.71 ⫻ 30 ⫻ 17.13/100 ⫽ 55.038 kJ.
“Nanostructured materials generated by high-intensity Quantity of material processed ⫽ 25 g.
ultrasound: sonochemical synthesis and catalytic studies”, Net energy supplied per unit weight of the material using the
Chemical Materials, Vol. 8 No. 8, pp. 2172-2179. 6-mm probe ⫽ actual energy delivered by horn during

222
 Ultrasound-assisted organic pigment dispersion Pigment & Resin Technology
N.P. Badgujar et al. Volume 44 · Number 4 · 2015 · 214 –223

sonication/quantity of material processed ⫽ 220.22 (kJ)/25 (g) ⫽ Time required for completion of dispersion ⫽ 30 min.
8.81 (kJ/g). Net energy delivered during the conventional method ⫽
Net energy supplied per unit weight of the material using the power input ⫻ time required
10-mm probe ⫽ actual energy delivered by horn during
⫽ 209.09 J/s ⫻ 1800 Sec. ⫽ 376363.63 J ⫽ 376.36 kJ
sonication/quantity of material processed ⫽ 168.75 (kJ)/25 (g) ⫽
6.75 (kJ/g).
Energy supplied in the form of heat to maintain the reaction
Net energy supplied per unit weight of the material using the temperature as 70°C ⫽ m.Cp,mix (Tprocess – TRef) ⫽ 25 ⫻
20-mm probe ⫽ actual energy delivered by horn during 4.0058 ⫻ (70 ⫺ 30) ⫽ 4005.8 J ⫽ 4.0058 kJ.
sonication/quantity of material processed ⫽ 55.038 (kJ)/25 (g) ⫽ Total energy supplied during conventional method ⫽ 380.36 kJ.
2.20 (kJ/g). Quantity of material processed ⫽ 25 g.
Net energy supplied for processing of material using
conventional method ⫽ net energy delivered during
Energy delivered during the conventional method
conventional method/quantity of material processed ⫽ 380.36
Voltage input to the homogeniser (Model RQ127 A/D, Remi
(kJ)/25 (g) ⫽ 15.21 (kJ/g).
Metals Gujarat Limited, India) ⫽ 230 V.
Current measured using a digital multimeter (MECO Model
9A06, MECO Meters Pvt. Ltd., Mumbai, India) ⫽ 1.1 A. Corresponding author
Downloaded by Indian Institute of Technology at Kanpur At 22:59 12 December 2016 (PT)

Power input to the homogeniser ⫽ voltage input ⫻ current S.H. Sonawane can be contacted at: shirishsonawane09@
measured ⫽ 230(V) ⫻ 1.1(A) ⫽ 209.09W. gmail.com

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 This article has been cited by:

1. Alexander Kraytsberg, Yair Ein-Eli. 2016. Conveying Advanced Li-ion Battery Materials into Practice The Impact of Electrode
Slurry Preparation Skills. Advanced Energy Materials 6:21, 1600655. [CrossRef]
2. S. Shaik, S. H. Sonawane, S. S. Barkade, Bharat BhanvaseSynthesis of Inorganic, Polymer, and Hybrid Nanoparticles Using
Ultrasound 457-490. [CrossRef]
Downloaded by Indian Institute of Technology at Kanpur At 22:59 12 December 2016 (PT)
 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)

Synthesis of Mica Doped Calcium Carbonate Filler for Partial

Replacement of Tio2 in Decorative Paint
Y. E. Bhoge, V. J. Patil, T. D. Deshpande, U. D. Patil and R. D. Kulkarni*
#
Department of Paint Technology, University Institute of Chemical Technology, North Maharashtra University,
Jalgaon (M.S.) India

Titanium dioxide (TiO2), being a prime pigment has fillers in paints and allied industries. Fillers are among
been used essential component in a paint formulation others barium sulphate, kaolin, calcium carbonate,
due to its excellent light scattering ability and high mica, silicates and silica [3]. The judicious
refractive index. The growing demand and the substitution of extender generally produces equivalent
increasing cost of TiO2 have driven the attention of hiding, tinting strength, stains, and scrub resistance.
paint technologists to search for its alternatives. Many The substitution of extenders not only helps to reduce
efforts have been made to partial replacement of the the cost but also helps to improve the properties, such
TiO2 with fine particle size extenders in paint as the flow and rheological movement under stress,
formulations. In present research work synthesis of gloss, leveling after application, mechanical and
mica doped calcium carbonate using co-precipitation impact resistance, hiding, reflectance, and brightness.
method in mixed flow reactor system is achieved. The An extender like high oil absorption calcined clay may
partial replacement of TiO2 pigment by various replace a part of titanium dioxide that demonstrates
percentages of Mica-CaCO3 filler in decorative paint true internal hiding and sheen control in flat wall
formulations has been made. Paint properties such as paints. The influence of extenders on the properties of
hiding power, scrub resistance, gloss, adhesion and paints has been studied extensively. The incorporation
weather resistance have been determined to establish of calcium carbonate and diatomaceous silica, or a
the optimum percentage of Mica-CaCO3 pigment in blend of micronized talc and dolomite in TiO2
the paint formulation. The optimum percentage of pigmented paints results in good color uniformity,
Mica-CaCO3 filler is about 20-30% by weight of TiO2 opacity, and washability. Similarly, the addition of
in paint formulations. The overall paint properties are finely ground extender to paints produces better
found to be satisfactory with cost cutting for dispersion, uniformity, colour, hiding, gloss, and
decorative paints. reflectance. The partial substitution of TiO2 by
extender barytes in alkyd based coatings exposed
Keywords— Mica-CaCO3 filler, mixed flow reactor outdoors and indoors by measuring properties like
system, co-precipitation method scratch hardness, gloss retention, tensile strength,
percent elongation, water vapour permeation, and
I. Introduction water absorption have been studied [4]. They have
Paints are used to protect the material surfaces against showed that paints pigmented solely with 30% PVC
various corrosions along with their decorative purpose. titanium dioxide can tolerate its replacement with a
In a dry film, in any case, there are just pigment barytes extender to the extent of 10% PVC. It was
particles and binder polymer fibers to keep the found that properties like adhesion, scratch hardness,
particles on the surface. As an ensuing, the minerals and tensile strength are not affected significantly in
utilized as a part of the paint formula the case of unweathered alkyd coatings in which TiO2
straightforwardly influence the attributes of the paint. is partly replaced by zinc oxide, talc, barytes, and
TiO2 is the most significant pigment for whiteness and china clay to the extent of 30% by weight.
a core pigment utilized as a part of the paints or Mica is a complex of hydrous potassium–aluminum
coatings. Then again, its high cost advances analysts silicate minerals which is differ in chemical
in paint industry to search for abundant and modest composition. Mica has a low coefficient of expansion,
substitutions. In waterborne paints some piece of the high dielectric strength, good electrical resistance, a
pigment is supplanted with filler so that cost of uniform dielectric constant and high capacitance
deciding item can be lessened with fillers/extenders. stability; at one time it was one the of best electrical
Various minerals are utilized with the point of and thermal insulators known. The most important
diminishing the expense and enhancing some physical application of mica is pearlescent pigments [5,6],
and mechanical properties of paints [1,2]. The which consist of transparent mica flakes coated on all
utilization of extenders must be carefully fitted to the sides with a thin layer of metal oxide, mostly titanium
formulation design of the paint or coating, as not dioxide. There are variety of methods for doping of
every extender will work successfully in every system. TiO2 onto mica flakes, including homogeneous
Filler/extender has an effect on gloss, texture, hydrolysis, titration, sol-gel technique, and chemical
suspension, tinting strength and viscosity of a paint. vapour deposition [7-10]. In present work synthesis of
Inert pigments, having a low refractive index and mica doped calcium carbonate achieved through co
being relatively inexpensive, are used as extenders or precipitation method in order to substitute the TiO2

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 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)

pigment in decorative water based paints. The particle Table 1 Water based Paint Formulations
size, morphology, phase and functional group
identification was carried out using FESEM, XRD and
FTIR analysis respectively. The colour strength of TiO2 Replace by % of mica-CaCO3 filler
Mica-CaCO3 was accomplished through colour Batch Batch Batch Batch
Sr. Batch
matching spectroscopy. Coatings properties such as Ingredients 2 3 4 5
No. 1
hiding power, gloss, scrub resistance, adhesion, pencil (5 %) (10%) (20%) (40%)
1 Water 20.1 20.1 20.1 20.1 20.1
hardness and mar resistance were performed as per
Propylene
ASTM and ISO standards. 2 0.8 0.8 0.8 0.8 0.8
Glycol
3 MIT- 111 0.3 0.3 0.3 0.3 0.3
II. Experimental Thickener
II.I Materials 4 Solution 0.2 0.2 0.2 0.2 0.2
Calcium nitrate tetrahydrate (Ca(NO3)2.4H2O), (3.5%)
Tween-80, Sodium carbonate (Na2CO3), Propylene 5
Borchi Gen
0.8 0.8 0.8 0.8 0.8
Glycol, Ammonia, were purchased from Merck WS
Specialties Pvt. Ltd. Mumbai. TiO2, Mica, Pine Oil, Antifoam k-
6 0.35 0.35 0.35 0.35 0.35
and Styrene Acrylic Emulsion (46%) were provided 35
by local supplier. Double distilled water was used as a Ammonia
7 0.15 0.15 0.15 0.15 0.15
sol.
medium for the preparation of Mica-CaCO3 Pigment.
Thickener
The free samples of Antifoam k-35, MIT- 111 and 8 Solution 0.1 0.1 0.1 0.1 0.1
Borchi Gen WS were supplied by K Tech India (3.5%)
limited, Thane and OMG Borchers, Germany. 9 TiO2 36.6 34.77 32.94 29.28 21.96
Mica-
10 - 1.83 3.66 7.32 14.64
Synthesis of Mica-CaCO3 pigment CaCO3
The co precipitation process was carried out by using Styrene
(1M) solutions of Calcium nitrate tetrahydrate Acrylic
11 37.0 37.0 37.0 37.0 37.0
Ca(NO3)2.4H2O as precursor and Sodium carbonate Binder
(Na2CO3) as precipitant in presence of non-ionic (46%)
surfactant such as Tween-80 were added dropwise 12 Silicon Oil 0.1 0.1 0.1 0.1 0.1
Borchi Gen
over a period of 60 min while at the bottom, 13 0.8 0.8 0.8 0.8 0.8
WS
suspension of water 100mL and mica 5.05 g with 14 Pine Oil 1.6 1.6 1.6 1.6 1.6
some sort of surfactant was taken. After the Propylene
completion of addition stirred the suspension for 30 15 0.8 0.8 0.8 0.8 0.8
Glycol
min; decant the supernatant liquid. Wash the Total 100 100 100 100 100
precipitate with distilled water and then dry at 60°C. It
was characterized on the basis of FTIR, density, oil
absorption and tinting strength analysis. Evaluation of the phase and morphology of Mica-
CaCO3 was conducted using D-8 Advance XRD of
Formulation of Water borne paint Brucker, Germany at 40 kV and a current of 30 mA
The experiments were carried out with lab dissolver with CuKα radiation (1.54060-1.54439). The
(Dispermat CV3, VMA-Getzmann GmbH) which assessment color was carried out using color matching
consists of a milling system and separate instrument spectrophotometer using D65 illuminant. The coatings
control case. The milling system exists as a double properties such as Gloss, pencil hardness, adhesion,
wall grinding chamber and a motor for the agitator in mar resistance, hiding power, and scrub resistance
the chamber. The essential dispersion parameters can were carried out using gloss meter, pencil hardness
be optimally and independently controlled via the tester (BYK Additive & Instruments, Germany), cross
control case. The actual particle size reduction in the cut adhesion tester, mar resistance tester, P-Fund
grinding chamber of a mill is accomplished by the Cryptometer, and Wet scrub resistance tester
moving material, which is activated by a high speed respectively as per their ASTM standards.
and high-energy agitator. The partial replacement with
Mica-CaCO3 pigment based decorative paint III. Results & Discussions
formulation was prepared as per the compositions Synthesis of Mica-CaCO3 Pigment
reported in Table 1. The synthesis was carried out using co precipitation
process which involves the slow addition of 1M
Characterizations solutions of Calcium nitrate tetrahydrate
The functional group analysis of Mica-CaCO3 was Ca(NO3)2.4H2O and Sodium carbonate (Na2CO3). Fig.
carried by using Shimadzu FTIR–8400 equipped with 1 shows the characteristic vibrations of alkyl chains in
KBr beam splitter and diffuses reflectance system surfactant which is adsorbed on the surface of mica-
(DRS). calcium carbonate. The bands at 2856 and 2926 cm–1
observed were ascribed to the symmetric and

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 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)

asymmetric vibrations of –CH2– and –CH3 groups. Gloss: The influence of replacement of TiO2 on the
The characteristics vibrations for calcite phase at 713 gloss of the surface coating is shown in fig. 3.
cm-1 was observed. The peaks at 1095 and 1026 cm-1 Addition of Mica-CaCO3 is more important on the
are assigned to Si-O stretching motions, and the peak gloss of the coating compared to other optical
at 913 cm-1 is believed to arise from an Al-OH-Al properties, since it increases significantly even with
bending. The peak at 699 cm-1 is likely the result of small additions of Mica-CaCO3. Replacement of TiO2
Al-O stretching [11] by Mica-CaCO3 affects negatively on the gloss of the
surface coating.

Fig. 1 FTIR of Mica-CaCO3 Fig. 3 Influence of replacement of TiO2 by Mica-

CaCO3 on Gloss of the surface coating
Coatings properties
Optical Properties: The CIELAB colour system is Mechanical and physical properties of coatings
Hiding Power: The phenomenon of hiding power is
the most suitable technique for measuring surface
based on refractive indices to have good hiding power
colour properties. The primary shading parameters
its refractive index needs to be much higher than that
dictated by the CIELAB shading framework are the
of the binder. The hiding power of prepared paint
parameters: L*, which speaks to softness on a size of 0
samples were carried out using P-Fund Cryptometer.
(dark) to 100 (unadulterated white); a* which is the
Mica-CaCO3 has a particle size and refractive indices
level of redness if positive or greenness it negative; b*
about the same as the TiO2 pigment; hence Mica-
which is the level of yellowness if positive or blueness
CaCO3 results in better efficiency of replacement and
if negative. Fig.2 shows gradually decrease in
can save about 20% in prime TiO2 pigment. Fig.4
whiteness with increase in % loading of Mica-CaCO3.
shows hiding power decreases with increase in %
For greater replacement of TiO2 by Mica-CaCO3 color
loading of Mica-CaCO3.
properties deteriorate significantly. This suggests that
Mica-CaCO3 can replace sufficiently TiO2 pigments in
emulsion paints. The evolution of yellowness index
(b*) with increasing replacement of TiO2 by Mica-
CaCO3 are shown in Fig.2. Yellowness index
decreases gradually with increasing Mica-CaCO3
content for some extent but at 40% loading it was
increased upto 0.799.

Fig. 4 Influence of replacement of TiO2 by Mica-

CaCO3 on Gloss of the surface coating

Wet Scrub test: It is directly related to washability

and stain removal, which is duly required for interior
latex paints. This test has been carried out with a wet
abrasion tester. The paint sample of 50 μm were
applied on a paper and dried for 96 hrs. These panels
were soaked in water for 10 min, followed by an
additional 5 min of soaking in 0.5% soap solution and
Fig. 2 Influence of replacement of TiO2 by Mica- were used for a scrub resistance test. The test panel
CaCO3 on whiteness and yellowness of the surface was mounted firmly on the plate, the soap-filled brush
coating was placed in a position, and the motor was started.
The addition of soap solution drops over the panel is

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 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016)

arranged at a fixed rate of 12 drops per min. [ASTM References

D-2486–69]. This test continued up to 2000 cycles. 1. McGonigle, F. et al., (1996), McGonigle, F., Ciullo, P.A.,
(edited by Ciullo P.A.), Paints & Coatings, Chapter 4 in
The samples loading upto 20% have passed the test.
Industrial Minerals and Their Uses, A Handbook & Formulary,
The mechanical properties of coated samples were Noyes Publication, Westwood New Jersey, P.125-136.
shown in Table 2. There is no remarkable effect of 2. Karakas, F. et al., (2010), Karakas, F.; Hassas, B. V.; Ozhan, K.;
properties such as mar resistance, dry film thickness, Boylu, F.; and Celik, M. S.; “Calcined kaolin and calcite as a
pigment and substitute for tio2 in water based paints”, XIV
pencil hardness, adhesion test, Wt/Lit, %NVM and
Balkan Mineral Processing Congress (BMPC 2012), Tuzla,
viscosity. Bosnia and Herzegovina; 06/2011
3. Laura, L. (2009), Laura, L., “combinations of titanium dioxide
Table 2 Water Based (Acrylic) paint testing and fillers in paints”, Degree Thesis, Satakunta University of
Applied Sciences,
Sr. Mica-CaCO3 loading
Test 4. Narayan, R.; Raju, K.V.S.N. (2000), Narayan, R.; Raju,
No. 0 5% 10% 20% 40% K.V.S.N., “The Use of Calcined Clay as Part Replacement of
A Wet film test Titanium Dioxide in Latex Paint Formulations”, Journal of
Fineness Applied Polymer Science, Vol. 77, Issue 5, pp. 1029–1036.
1 of 7+ 7+ 7+ 7+ 7+ 5. Maisch, R. et al., (1996), Maisch, R.; Stahlecker, O.; Kieser M.;
grinding “Mica pigments in solvent free coatings systems”, Progress in
2 Wt / litre 1.36 1.37 1.31 1.33 1.34 Organic Coatings, vol. 27, Issue 1–4, pp. 145-152
6. Levis, P. A., Pigment Handbook., Wiley Interscience, 1998, 55-
3 % NVM 41.66 41.66 41.66 41.66 41.66 90
Visocity 7. Pfaff G. (2009) Special effect pigments. High performance
4 35 40 35 36 40
(Sec) pigments. Wiley-VCH Verlag GmbH & Co. KGaA;. pp. 75-104.
B Dry film test 8. Bayat N. et al., (2008), Bayat, N.; Baghshahi, S.; Alizadeh, P.;
Pencil “Synthesis of white pearlescent pigments using the surface
1 3B 3B 4B 4B 3B response method of statistical analysis”, Ceram Int, Vol. 34,
Hardness
Issue 8, pp. 2029-2035.
1200 1200 1200 1200 1200 9. Hildenbrand, V. D., et al., (1997), Hildenbrand, V. D.; Doyle,
Mar
2 Pass Pass Pass Pass Pass S.; Fuess, H.; Pfaff, G.; Reynders, P.; “Crystallisation of thin
Resistance
(Red) (Red) (Red) (Red) (Red) anatase coatings on muscovite”, Thin Solid Films, Vol. 304,
45- Issue1-2, pp. 204-211.
3 DFT 45-50 40-45 40-45 45-50 10. Cho, J. H.; Lim, S. H.; (2006), Cho, J. H.; Lim, S. H.;
50
3B 3B 3B 3B 2B “Internal structure analysis of mica particles coated with metal
Cross cut oxide by transmission electron microscopy”, Dyes Pigm, Vol.
4 (5- (5- (5- (5- (15-
adhesion 69, Issue 3, pp. 192-195.
15%) 15%) 15%) 15%) 35%) 11. Zhang, Y.H. et al., (2005), Zhang, Y.H.; Dang, Z. M.; Xin, J.
H.; Daoud, W. A.; Liu, J. J. Y.; Fei, B.; Li, Y.; Wu, J.; Yang, S.;
IV. Conclusions Li, L. F.; “Dielectric Properties of Polyimide-Mica Hybrid
Films”, Macromol. Rapid Commun., vol. 26, pp. 1473–1477,
In the summery, the preparation of mica-CaCO3 was DOI: 10.1002/marc.200500310
successfully carried out using co precipitation reaction
and utilized in the formulation of durable decorative
coatings. The decorative coatings formulated using
mica-CaCO3 shows better physical, mechanical and
chemical resistance properties as per required
standards. The faster reactive events under ambient
conditions, stabilized crystal growth, higher yield of
mica-CaCO3. Thus, mica-CaCO3 was found as an
acceptable substitution for TiO2 since its contribution
to superior opacity and hiding power. As a result of
the investigation, 20% of TiO2 can be substituted with
mica-CaCO3 without any adverse effect on main paint
properties of which economical beneficiations has
been explained.

Acknowledgements
Financial assistance under the scheme of Technical
Education Quality Improvement Programme-II
(TEQIP-II), MHRD, New Delhi is acknowledged. The
authors are grateful to Central Instrumentation
Laboratory, University Institute of Chemical
Technology, North Maharashtra University, Jalgaon
(MS) India for providing FESEM, XRD, Colour
matching spectrophotometer and FTIR facilities.

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