Synthesis and characterization of copper phthalocyanine and tetracarboxamide copper phthalocyanine deposited mica-titania pigments

Article abstract of DOI:10.1016/j.dyepig.2012.06.010

Combination pigments were synthesized by the deposition of copper phthalocyanine and tetracarboxamide copper phthalocyanine on a mica-titania pigment in dimethyl formamide solvent to improve color properties. The FT-IR and XRD analyses were performed to observe the crystal transformations of the pigments on the substrate. The stable beta form of copper phthalocyanine normally preferred in paint applications was obtained at 90 °C and 120°C, while tetracarboxamide copper phthalocyanine remained amorphous at all temperatures experimented. Pigment surface morphologies were investigated by SEM analysis. Copper phthalocyanine crystalline rods were observed on the mica-titania substrate, however, the tetracarboxamide copper phthalocyanine pigment did not exhibit any such crystalline structure due to its amorphous structure, which was confirmed by XRD analysis. Furthermore, nitrogen elemental analysis was performed to determine the amount of copper phthalocyanines adsorbed to the mica-titania surfaces at different temperatures. The resulting combination pigments showed enhanced luster, good dispersion, hue, and high color intensity.

Full text of DOI:10.1016/j.dyepig.2012.06.010

Dyes and Pigments 96 (2013) 31e37
Contents lists available at SciVerse ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Synthesis and characterization of copper phthalocyanine and tetracarboxamide
copper phthalocyanine deposited mica-titania pigments
,
c
d
Berna Burcu Topuz a, Güngör Gündüz b , Bora Mavis , Üner Çolak
*
a
ꢀ
Polimer Bilim ve Teknolojisi Bölümü, Orta Dogu Teknik Üniversitesi, Ankara 06531, Turkey
Kimya Mühendisligi Bölümü, Orta Dogu Teknik Universitesi, Ankara 06531, Turkey
Makina Mühendisligi Bölümü, Hacettepe Üniversitesi, Beytepe, Ankara 06800, Turkey
Nükleer Enerji Mühendisligi Bölümü, Hacettepe Üniversitesi, Beytepe, Ankara 06800, Turkey
b
ꢀ
c
ꢀ
d
ꢀ
a r t i c l e i n f o
a b s t r a c t
Article history:
Combination pigments were synthesized by the deposition of copper phthalocyanine and tetracarbox-
amide copper phthalocyanine on a mica-titania pigment in dimethyl formamide solvent to improve color
properties. The FT-IR and XRD analyses were performed to observe the crystal transformations of the
pigments on the substrate. The stable beta form of copper phthalocyanine normally preferred in paint
applications was obtained at 90 ꢀC and 120 ꢀC, while tetracarboxamide copper phthalocyanine remained
amorphous at all temperatures experimented. Pigment surface morphologies were investigated by SEM
analysis. Copper phthalocyanine crystalline rods were observed on the mica-titania substrate, however,
the tetracarboxamide copper phthalocyanine pigment did not exhibit any such crystalline structure due
to its amorphous structure, which was confirmed by XRD analysis. Furthermore, nitrogen elemental
analysis was performed to determine the amount of copper phthalocyanines adsorbed to the mica-
titania surfaces at different temperatures. The resulting combination pigments showed enhanced
luster, good dispersion, hue, and high color intensity.
Received 1 November 2011
Received in revised form
14 June 2012
Accepted 18 June 2012
Available online 16 July 2012
Keywords:
Effect pigments
Combination pigment
Mica-titania
Copper phthalocyanine
Combination pigment
Beta polymorph
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
It is reported that the metastable
morphic transition to the stable
a-polymorph undergoes a poly-
b
-polymorph when heated over
Phthalocyanine is a planar 18
p-electron heterocyclic aromatic
250 ꢀC or treated with some aromatic hydrocarbons like xylene
system with alternating nitrogen-carbon atom ring structure
derived from porphyrin [1]. Phthalocyanines have been known for
more than 70 years and have been extensively used as colorants
[2e4]. Moreover, they have attracted interest for a variety of uses
such as liquid crystals, photosensitizers, non-linear optics, solar
cells, catalysis, and in various chemical sensing applications [5]. The
peripheral and non-peripheral positions on the benzenoid ring of
phthalocyanines can be substituted with many other molecules to
impart new properties. In addition, over seventy different metal ions
can be introduced into the central cavity to improve physical
properties to suit a desired technological application [3,6]. Among
them, copper phthalocyanine is one of the most important classes of
colorants and has superior properties such as light fastness, tinting
strength, covering power, and resistance to alkalis and acids [7].
Copper phthalocyanine exists in many polymorphic forms
[8e10]. This transformation is not a simple process, but the
metastable powder grows to
changing its crystal structure before the actual transformation
takes place [11]. The resulting -polymorph is in a relatively larger
crystalline form [10,12]. The transformation of the pigment
a considerable extent without
b
a/b
can take place in paint formulations because many organic liquids
used as thinners and diluents can induce this transformation.
Large crystals change the shade and the tinctional strength of the
paint in a storage period between the preparation of the compo-
sition and its final use [13,14]. For these reasons, the
b-form is
preferred in industrial use.
The synthesis of metal phthalocyanines is usually achieved in
high yields by cyclotetramerization of phthalonitrile, diiminoi-
soindoline, phthalic anhydride or phthalimide in the presence of
a metal salt at high temperatures [15,16]. In order to synthesize
peripherally or nonperipherally functionalized phthalocyanines,
precursors with desired substituents can be used. Phthalocyanines
can be produced in the medium of solvents or under microwave
irradiation. In the last decade, an increased interest has been
focused on the application of microwave irradiation in their
and the most commonly studied phases are alpha (a) and beta (b).
* Corresponding author. Tel.: þ90 312 2102616; fax: þ90 312 2101264.
E-mail address: ggunduz@metu.edu.tr (G. Gündüz).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2012.06.010

32
B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
synthesis. Numerous reactions can be performed under microwave
assisted conditions in which significant rate enhancements,
improved yield and selectivity, and a reduction in thermal by-
products have been achieved [17,18]. In particular, the reaction
time and energy input are supposed to be mostly reduced in the
reactions which last for a long time at high temperatures under
conventional conditions [17,19]. Copper phthalocyanine (CuPh) and
tetracarboxamide copper phthalocyanine (TCuPh) were also
synthesized in this research work under microwave irradiation
conditions of reactants.
Phthalocyanines are absorption pigments which possess very
high surface energy, and therefore, tend to self-agglomerate to
form coarser particles in paint formulations or in other applications
[20]. The agglomerated particles are generally mechanically
crushed into smaller particles or under high shear mixing, and
ultrasonic dispersion can also be performed to break the agglom-
erates [21,22]. The surface of the crushed pigment particles can also
be chemically treated to enable the individual particles to stay in
a stable dispersed state. However, when stored for an extended
period of time the pigment particles can again agglomerate and
adversely affect the color.
The use of phthalocyanines together with other pigments to
make the so called ‘combination pigment’ can yield new pigments
with enhanced properties. When phthalocyanine pigments are
imparted on ‘effect pigments’ one can obtain new pigments with
excellent spreading properties, brilliant colors, high color intensity,
gloss, and stability. Most effect pigments are titania coated mica
pigments, and they depict excellent brilliant colors.
Combination pigments can be produced by the deposition of
absorption pigments (or dyes) on the surface of a flaky substrate
coated with a metal oxide whereby pigment particles adhere
quickly. The combination of two pigments can exhibit satisfactory
spreading properties, high color effect, and good color saturation
[21]. Additionally, the tendency of absorption pigment particles to
flocculate is also eliminated or greatly reduced when the particles
are bound onto the substrate surfaces. Furthermore, absorption
pigments have high color intensity, light fastness, and bleed resis-
tance properties which make the resulting combination pigments
suitable for automobile finishes and other paint applications. As
a flaky substrate, pearlescent pigments of titania coated on mica are
of particular interest because the color is derived entirely from the
interference effect. They make possible combination pigments with
the widest range of colors [22].
There are very few patent studies related to the synthesis of
combination pigments. These studies are quite complex since they
involve several steps and components to synthesize the desired
combination pigment. For example, milling was needed to disperse
a phthalocyanine pigment in water, and/or additives were used to
prevent the coagulation of the pigment and improve compatibility.
All of these additional steps are time consuming, and detract from
the economic feasibility of the pigment.
The main objective of this work is to synthesize combination
pigments including mica-titania as a pearlescent pigment and CuPh
and TCuPh as absorption pigments. In this method, because the
phthalocyanines were soluble in DMF, no additional dispersing
agents or processing steps were required; in addition, no compat-
ibility binders were needed to adhere the phthalocyanines onto
mica surfaces. Simple stirring of the dispersed phthalocyanines
with mica-titania pigment gives the desired combination pigments
with enhanced gloss, hue, and color properties. Furthermore,
agglomeration of phthalocyanine molecules confronted in indus-
trial applications was eliminated by the deposition of these parti-
cles onto the mica-titania substrate. CuPh and TCuPh were used to
synthesize combination pigments at different temperatures, and
crystalline forms of phthalocyanines on mica-titania surfaces were
investigated. The desired stable
deposited onto the substrate.
b-form of CuPh was successfully
2. Experimental
2.1. Materials
Mica-titania was synthesized according to the reported proce-
dure [23]. Analytical grade phthalic anhydride, trimellitic anhy-
dride, ammonium molybdate, urea, copper (II) chloride, sodium
hydroxide (NaOH), hydrochloric acid (HCl), and dimethyl form-
amide were used in the experiments.
2.2. Preparation
2.2.1. Synthesis of copper phthalocyanine pigments
2.2.1.1. Synthesis
of
copper
phthalocyanine
(CuPh). Urea
(0.092 mol), phthalic anhydride (0.018 mol), copper (II) chloride
(0.005 mol), and ammonium molybdate (0.0596 mol) were ground
for 30 min in an agate mortar. The mixture was put into a flask and
wetted with distilled water (5 mL). It was then heated in a micro-
wave oven at 600 W for 5 min. The crude product was purified by
washing in sequence with hot water (70 ꢀC), 6 M HCl, 1 M NaOH,
and with hot water again followed by filtration. After these steps,
the pigment was washed with ethanol and filtered until the filtrate
was colorless. The resulting pigment was dried in an oven at 100 ꢀC.
2.2.1.2. Synthesis of tetracarboxamide copper phthalocyanine
(TCuPh). Urea (0.092 mol), trimellitic anhydride (0.018 mol),
copper (II) chloride (0.005 mol), and ammonium molybdate
(0.0596 mol) were used and treated as above, excluding only the
washing step with NaOH solution.
2.2.2. Synthesis of combination pigments
2.2.2.1. Synthesis of copper phthalocyanine deposited mica titania
pigment (CuPhM). The preparation of combination pigment was
carried out by mixing CuPh with mica-titania pigment in DMF
solvent. For this purpose, titania coated mica with the highest rutile
content was used [23]. First, CuPh (40 mg, 6.9 ꢁ 10ꢂ5 mol) was
dissolved in DMF (10 mL) while mixing the solution, mica-titania
pigment (0.3 g) was added and stirred for an hour. The suspen-
sion was then filtered and washed with DMF. In order to remove
any free CuPh, the wet cake was suspended in DMF and the CuPhM
particles were allowed to settle and the supernatant DMF con-
taining the CuPh was removed from the solution. In order to get rid
of free CuPh particles, the wet cake was suspended in DMF and kept
for a while to settle down CuPhM particles while the supernatant
liquid containing free CuPh particles was removed from the solu-
tion. This process was repeated until the supernatant liquid was
colorless. The wet cake was filtered and dried at 90 ꢀC in an oven.
CuPh deposited mica pigments were synthesized at different
temperatures of 25 ꢀC, 60 ꢀC, 90 ꢀC, and 120 ꢀC.
2.2.2.2. Synthesis of tetracarboxamide copper phthalocyanine
deposited mica titania pigment (TCuPhM). The same procedure in
Section 2.2.2.1 was applied except TCuPh (52 mg, 6.9 ꢁ 10ꢂ5 mol)
was used instead of CuPh for the deposition. TCuPh deposited mica
pigments were also synthesized at different temperatures which
are 25 ꢀC, 60 ꢀC, 90 ꢀC, and 120 ꢀC.
2.3. Analysis
The chemical structure of the copper phthalocyanine pigments
CuPh and TCuPh and the derived combination pigments were
identified by FT-IR spectroscopy (IR Prestige-21 SHIMADZU). The

B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
33
crystal structures of copper phthalocyanines and combination
pigments were determined by XRD analysis (RIGAKU-D/Max-2200/
N stretching, 1328 cmꢂ1 for C-C stretching in isoindole, 1093 cmꢂ1
for CeH in plane deformation and at 738 cmꢂ1 for CeH out of plane
deformation of phenyl ring which differed from CuPh to some
extent due to substitution. TCuPh also shows additional bands that
do not exist in the CuPh spectrum due to its four amide groups
bonded to peripheral benzenoid rings of the macrocycle. These
PC). The XRD analysis was carried out by using CuK
a
(
l
¼ 0.154 nm)
radiation operated at 40 kV and 20 mA for the crystal structure
determination of CuPh and TCuPh on mica-titania surfaces. The
XRD patterns were recorded in the 2q
range from 5ꢀ to 40ꢀ with
a step size of 0.02ꢀ. Elemental (nitrogen) analysis (LECO, CHNS-932)
was performed to determine the amounts of CuPh and TCuPh
deposited on mica surfaces. The elemental analyzer offers simul-
taneous multi-elemental determination of carbon, hydrogen,
nitrogen, and sulfur in homogenous microsamples (2 mg). SEM
(Quanta 400F Field Emission) was used to examine the morphology
of phthalocyanines on mica-titania surfaces. The measurements
were undertaken in high vacuum mode of the instrument and the
samples were coated with 10 nm Au/Pd.
peaks include NeH stretching bands at 3317 cmꢂ1 and 3167 cmꢂ1
C]O stretching of the amide at 1656 cmꢂ1, and NeH bending
combined with CeN stretching at 1583 cmꢂ1
,
.
3.2. SEM micrographs of combination pigments
The SEM micrographs of the copper phthalocyanines coated
mica-titania (CuPhM) pigments at different temperatures are
shown in Fig. 3. On the surface of the mica-titania pigments rod-
like crystallites with variable sizes can be observed in different
samples. A discussion on structural analysis of these rods will be
given in Section 3.5. In order to determine quantitatively the
increase in the lengths of the rods, the average lengths of the
crystallites were calculated and the results are presented in Table 1.
It is worth mentioning here that there is a growth trend in the sizes
of the rods with an increase in reaction temperature.
In Fig. 4, the SEM micrographs of TCuPhM synthesized at
different temperatures are shown. In the SEM micrographs
evidence of formation of TCuPhM pigment crystallites could not be
found since there was no obvious morphological difference
between the pigment coated surfaces and the pristine mica-titania
surfaces. The crystallite growth may have been prevented by the
amide branches of TCuPh.
2.4. Determination of optical properties
The optical properties of pigments synthesized were deter-
mined by incorporating them in a paint formulation. For this
purpose a long oil alkyd resin (60% resin þ 40% white sprit) (Betek)
was used. The paint was formulated as 89.52% by weight alkyd
(resin), 7.96% white sprit (solvent), 0.31% cobalt naphtenate (drier),
0.24% lead naphtenate (drier), and 2% CuPhM or TCuPhM
(pigment). The gloss values of paints having CuPhM or TCuPhM
pigments were determined by using a gloss meter (Rhopoint, Novo-
Gloss). The colors of the paints (i.e. L*a*b* values) were determined
by using a color measuring device (Datacolor 400).
3. Results and discussion
3.3. Elemental analysis of combination pigments
3.1. FT-IR spectroscopy of copper phthalocyanines
Nitrogen elemental analyses were performed for the combina-
tion pigments in order to determine the effect of temperature on
the deposition of copper phthalocyanines onto the mica-titania
substrates. Table 2 shows mass percentages of CuPh and TCuPh
pigments on the substrate at different temperatures. A significant
increase in the amount of CuPh on the substrate occurred with the
increase of temperature. However, the amount of CuPh was found
to decrease slightly at 120 ꢀC compared to that at 90 ꢀC; probably
some desorption occurs at 120 ꢀC. Although equal moles of TCuPh
and CuPh were used in the combination pigment synthesis, lower
amounts of TCuPh deposited on the substrate. Furthermore, the
The FT-IR spectrum of CuPh is given in Fig. 1. It has characteristic
peaks at 3041 and 2910 cmꢂ1 for aromatic CeH stretching,
1610 cmꢂ1 for C]C macrocycle ring deformation,1506 cmꢂ1 for C]
N stretching, 1333 cmꢂ1 for CeC stretching in isoindole, 1091 cmꢂ1
for CeH in plane deformation, and 723 cmꢂ1 for CeH out of plane
deformation of phenyl. The other peaks at 1286 cmꢂ1, 1165 cmꢂ1
and 1119 cmꢂ1 correspond to CeN stretching in isoindole, C-N in
plane bending, C-H in plane bending, respectively.
The FT-IR spectrum of TCuPh is given in Fig. 2. It has charac-
teristic peaks at 3037 and 2912 cmꢂ1 for aromatic CeH stretching,
1614 cmꢂ1 for C]C macrocycle ring deformation,1504 cmꢂ1 for C]
Fig. 1. FT-IR spectrum of copper phthalocyanine (CuPh).
Fig. 2. FT-IR spectrum of tetracarboxamide copper phthalocyanine (TCuPh).

34
B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
Fig. 3. SEM micrographs of CuPhM at (a) 25 ꢀC, (b) 60 ꢀC, (c) 90 ꢀC, (d) 120 ꢀC.
amount of deposition of TCuPh as a function of temperature was
inconsistent (Table 2).
forms of CuPh are deposited onto the substrate at 60 ꢀC. At 90 ꢀC
and 120 ꢀC, only -peaks could be observed at 729 cmꢂ1, and in
addition, a
-peak at 781 cmꢂ1 was also present.
b
b
Fig. 6 shows the FT-IR of TCuM pigments synthesized at different
temperatures. The peaks of TCuM were hardly distinguishable,
because, very small amounts of TCuPh deposited on the substrates.
3.4. FT-IR spectra of combination pigments
The peaks appearing at 1190 cmꢂ1, 941 cmꢂ1, 871 cmꢂ1
864 cmꢂ1, 771 cmꢂ1, and 723 cmꢂ1 in the IR spectrum in Fig. 1
confirms that CuPh synthesized is in -phase [9]. However, peaks
corresponding to the -phase can also be seen with very small
,
The polymorphic form of TCuPh powder was found to be a-phase
which was confirmed by peaks at 769 cmꢂ1, and 723 cmꢂ1. The peak
at 723 cmꢂ1 became significant when the broad peak at 739 cmꢂ1
was deconvoluted. The peaks observed at 739 cmꢂ1 and 715 cmꢂ1
belong to the out of plane deformation of the macrocycle. In TCuM
a
b
intensity at 779 cmꢂ1 and 984 cmꢂ1. In the case of the CuPhM
pigments, a peak shift was observed with increasing temperatures.
Fig. 5 shows the FT-IR spectra of CuPh and CuPhM pigments in
700e900 cmꢂ1 range.
pigments, no
a and b peaks of TCuPh were observed at the
temperatures the experiments carried out. So it can be interpreted
that the TCuPh formed an amorphous structure on the mica-titania
substrate.
The most distinguishable peaks of CuPh corresponding to
-forms are at 723, and 729 cmꢂ1, respectively [9]. The CuPh is
found to be in the -phase on mica-titania pigment when deposited
a- and
b
a
at 25 ꢀC as confirmed by the -peak at 723 cmꢂ1. As the deposition
a
3.5. XRD analysis of combination pigments
temperature is increased to 60 ꢀC, the peak at 723 cmꢂ1 broadened
and created an additional peak at 729 cmꢂ1. In fact, this broadened
In Fig. 7, the XRD peaks of CuPh located at 2
q
¼ 6.86ꢀ, 9.74ꢀ, and
15.6ꢀ all belong to the
a-form. A small peak due to the b-form is
peak contains both a- and b-peaks. In other words, both a- and b-
present at 2
q
¼ 9.16ꢀ. At 25 ꢀC, the CuPh pigment on the surface of
the mica-titania showed pure a-polymorphic phase with peaks at
Table 1
2q
¼ 6.82ꢀ and 15.68ꢀ. When the reaction temperature was
Average length of CuPh rods at different temperatures.
increased to 60 ꢀC, tiny peaks of
b-phase were also observed in the
Sample
Average length of rods (mm)
pattern. This feature suggests that the CuPh on the mica-titania
substrate begins to transform to the -form at this temperature.
In fact it was stated in the literature that the metastable -poly-
morph tends to transform to the stable -form by thermal treat-
ment or by exposure to some organic solvents [12]. When the
CuPhM (25 ꢀC)
CuPhM (60 ꢀC)
CuPhM (90 ꢀC)
CuPhM (120 ꢀC)
2.50
3.63
6.09
b
a
b
10.94

B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
35
Fig. 4. SEM micrographs of TCuPhM at (a) 25 ꢀC, (b) 60 ꢀC, (c) 90 ꢀC (d) 120 ꢀC.
temperature was further increased to 90 ꢀC, the peaks that are
d ¼ 12.88 Å. A shift to the larger interplanar spacing between the
(200) planes could be due to an increase of distance between TCuPh
molecules affected by amide side groups.
When the XRD pattern of TCuPhM pigments was investigated,
no peaks could be clearly detected. So, it is clear that the TCuPh
deposited on mica-titania substrate had an amorphous structure at
all deposition temperatures. This may be because the amide groups
prevented ordering (stacking) of molecules as crystals on the
ascribed to the
showed up distinctly at 2
crystalline form is also identifiable at 2
precise analysis of data, as, these peaks cannot be clearly seen in
Fig. 7.
a-crystalline form disappeared, and the b-peaks
q
¼ 7.02ꢀ and 9.16ꢀ. At 120 ꢀC, the
b-
q
¼ 6.98ꢀ and 9.14ꢀ from the
The XRD patterns of TCuPh pigment show a structure similar to
the
a
-polymorphic form of CuPh and peaks appear at 2
q
¼ 6.88ꢀ,
7.22ꢀ, and 15.9ꢀ as seen from Fig. 8. While the former one is iden-
tifiable, the latter two are less significant. Upon deconvolution of
2
q
¼ 5ꢀe10ꢀ range, extremely broad and small peaks at 2
q
¼ 6.88ꢀ
and 7.22ꢀ were identified. The most intense peak located at
2
q
¼ 5.58ꢀ corresponds to an interplanar spacing of d ¼ 15.83 Å.
This peak is the third peak that is obtained in the deconvolution of
the 2
(200) plane of TCuPh. Such a peak is expected to appear at
2
q
¼ 5ꢀe10ꢀ range in the Peakfit software. It is thought to be the
q
¼ 6.88ꢀ which corresponds to a smaller interplanar spacing of
Table 2
Mass percentages of CuPh and TCuPh pigments on mica-titania.
Sample
Phthalocyanine (mass%)
CuPhM (25 ꢀC)
CuPhM (60 ꢀC)
CuPhM (90 ꢀC)
CuPuM (120 ꢀC)
TCuPhM (25 ꢀC)
TCuPhM (60 ꢀC)
TCuPhM (90 ꢀC)
TCuPhM (120 ꢀC)
4.26
7.30
8.12
7.76
3.08
0.71
1.83
1.92
Fig. 5. FT-IR spectra of (a) CuPh, (b) Mica titania, CuPhM pigment at (c) 25 ꢀC, (d) 60 ꢀC,
(e) 90 ꢀC, (f) 120 ꢀC.

36
B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
Fig. 6. FT-IR spectra of, (a) TCuPh, (b) Mica titania, CuPhM pigment at (c) 25 ꢀC, (d)
60 ꢀC, (e) 90 ꢀC, (f) 120 ꢀC.
substrate by increasing the distance between the molecules. On the
contrary, the interaction between the TCuPh molecules and mica-
titania substrate must have been greater than the interaction of
TCuPh molecules among themselves. This would lead to higher
adhesive force between the deposit and the substrate. Accordingly,
deposition is expected to occur at a higher nucleation rate yielding
an amorphous fine-grain structure in the growth stage.
Fig. 8. XRD patterns of (a) TCuPh, (b) Mica titania, TCuPhM pigment at (c) 120 ꢀC, (d)
90 ꢀC, (e) 60 ꢀC, (f) 25 ꢀC.
whereas TCuPh was changed between 0.0065 and 0.052 g. In all the
characterizations given above CuPhM specimen prepared by using
0.040 g CuPh and TCuPhM specimen prepared by using 0.052 g
TCuPh were used (see Section 2.2.2.1).
The dependence of gloss on the initial amount of CuPh or TCuPh
used in the synthesis of combination pigments is given in Table 3
where the numbers after the symbols indicate the initial amounts
- used. Small quantities of CuPh (or TCuPh) increase the gloss of
titania-mica pigment at all scattering angles. The increased amount
of CuPh (or TCuPh) may cause absorption of light which in turn
causes a decrease in gloss.
The L*a*b* is an important parameter for the characterization of
optical properties of the pigments; specifically, L* is the lightness,
a* is red or green, and b* is yellow or blue; that is, a* and b* are color
opponent dimensions. dL*, da* and db* indicate how much a stan-
dard and a sample differ from one another in L*, a* and b*. dE*
represents the total color difference found from Euclidean distance,
such that,
3.6. Optical properties
CuPhM and TCuPuM pigments synthesized at 90 ꢀC were used in
an alkyd resin to study their optical behavior. The paint formulation
was given in Section 2.4. The gloss values were measured at angles
of 25ꢀ, 60ꢀ, and 85ꢀ which are the three basic angles used in the
measurements. In order to examine the effect of process conditions
on optical properties the amount of CuPh or TCuPh dissolved in
DMF was varied. CuPh was changed between 0.005 and 0.040 g
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
E*z2:3 corresponds to a noticeable difference. In Table 4, dL*,
ꢀ
ꢁ
ꢀ
ꢁ
2
2
À
Á
2
D
E*
¼
L*2 ꢂ L*1 þ a*2 ꢂ a1* þ b2* ꢂ b*1
D
da*, db* and dE* values are given for each pigment. The increase of
the initial amount of CuPh or TCuPh used in the synthesis increases
the dL*, da*, db* and dE* values reaching the highest values at the
highest amounts of CuPh and TCuPh, i.e. in CuPhM040 and
Table 3
Gloss values of paints including CuPhM and TCuPhM pigments.
Specimen
25ꢀ
60ꢀ
85ꢀ
Mica-titania (Rutile)
CuPhM 005
CuPhM 010
CuPhM 020
CuPhM 040
TCuPhM 0065
TCuPhM 0130
TCuPhM 0260
TCuPhM 0520
48.5
58.7
56.7
50.7
49.8
59.8
48.0
47.3
45.9
75.7
79.6
78.9
78.5
78.0
84.9
75.2
74.8
74.0
75.8
80.8
78.8
77.6
77.2
87.6
58.0
50.1
45.3
Fig. 7. XRD patterns of, (a) CuPh, (b) Mica titania, CuPhM pigment at (c) 120 ꢀC, (d)
90 ꢀC, (e) 60 ꢀC, (f) 25 ꢀC.

B.B. Topuz et al. / Dyes and Pigments 96 (2013) 31e37
37
Table 4
combination pigments depicted enhanced gloss especially at lower
amounts of depositions.
The dL*, da*, db*, and dE* values of paints containing combination pigments.
Specimen
dL*
0.00
da*
0.00
db*
0.00
dE*
0.00
1.74
3.18
6.00
8.75
15.28
17.25
21.77
TCuPhM0065 (standard)
TCuPhM0130
TCuPhM0260
TCuPhM0520
CuPhM005
CuPhM010
CuPhM020
CuPhM040
Acknowledgments
0.00
ꢂ2.13
ꢂ5.12
ꢂ3.80
ꢂ8.92
ꢂ11.48
ꢂ16.09
0.10
1.65
1.69
5.26
7.23
7.61
10.66
ꢂ1.73
ꢂ1.70
Authors would like to thank Kaltun Madencilik A.S¸ . for
providing the mica flakes used in the work and acknowledge the
ꢂ3.97
ꢂ5.87
ꢂ10.07
ꢂ10.38
ꢂ10.06
ꢀ
partial financial support provided by the Orta Dogu Teknik Ünver-
sitesi (Grant No: BAP-07-02.2009.00.01).
References
[1] Alkan C, Aras L, Gündüz G. Synthesis, characterization, and electrical prop-
erties of diazophenylene bridged Co, Ni, Cu, Ce, and Er phthalocyanine poly-
mers. J App Polym Sci 2007;106:378e85.
[2] Kalkan A, Bayir ZA. Phthalocyanines with rigid carboxylic acid containing
pendant arms. Polyhedron 2006;25:39e42.
[3] Kulaç D, Bulut M, Altindal A, Özkaya AR, Salih B, Bekaroglu Ö. Synthesis and
characterization of novel 4-nitro-2-(octyloxy)phenoxy substituted symmet-
rical and unsymmetrical Zn(II), Co(II) and Lu(III) phthalocyanines. Polyhedron
2007;26:5432e40.
[4] Akdemir N, Erdem G. Synthesis and characterization of novel phthalocyanines
containing (n-octyl) mercapto acetamid substituents. Synth React Inorg
Metal-Org Nano-Metal Chem 2005;35:819e24.
[5] Verdree V, Pakhomov S, Su G, Allen M, Countryman A, Hammer R, et al. Water
soluble metallo-phthalocyanines: the role of the functional groups on the
spectral and photophysical properties. J Fluorescence 2007;17:547e63.
[6] Sesalan BS, Koca A, Gül A. Water soluble novel phthalocyanines containing
dodeca-amino groups. Dyes Pigm 2008;79:259e64.
[7] Marvel CS, Rassweiler JH. Polymeric phthalocyanines. J Amer Chem Soc 2002;
80:1197e9.
[8] Prabakaran R, Kesavamoorthy R, Reddy GLN, Xavier FP. Structural investiga-
tion of copper phthalocyanine thin films using X-ray diffraction, Raman
scattering and optical absorption measurements. Physica Status Solidi (B)
2002;229:1175e86.
[9] Patil KR, Sathaye SD, Hawaldar R, Sathe BR, Mandale AB, Mitra A. Copper
phthalocyanine films deposited by liquid-liquid interface recrystallization
technique (LLIRCT). J Coll Interface Sci 2007;315:747e52.
[10] Emeleus HJ, Sharpe AG. Advances in inorganic chemistry and radiochemistry,
vol. 7. Academic Press; 2008.
[11] Iwatsu F, Kobayashi T, Uyeda N. Solvent effects on crystal growth and trans-
formation of zinc phthalocyanine. J Phys Chem 1980;84:3223e30.
[12] Iwatsu F. Size effects on the alpha-beta transformation of phthalocyanine
crystals. J Phys Chem 1988;92:1678e81.
[13] Graham DP. Inventor; EI du Pont de Nemours and Company, assignee. Process
of producing tinctorially stable phthalocyanine coloring matters, US patent
2556530; 1951 June 12.
Fig. 9. The comparative color properties of combination pigments based on different
phthalocyanine deposition.
[14] Howell ET. Inventor; EI du Pont de Nemours and Company, assignee.
Production of phthalocyanine colors in pigmentary state. US patent 2816115;
1957 Dec 10.
[15] McKeown NB. Phthalocyanine-containing polymers. J Mater Chem 2000;10:
1979e95.
[16] Agboola BO. Catalytic activities of metallophthalocyanines towards detection
and transformation of pollutants, Ph.D. thesis, Rhodes University, 2007.
[17] Seven O, Dindar B, Gultekin B. Microwave-assisted synthesis of some metal-
TCuPhM052, respectively. It is clearly seen that CuPhM040 has
a much stronger effect on the change of color than TCuPhM040.
The change of comparative color properties can be better seen
from Fig. 9 where the pigments were located on an a*ꢂb* diagram.
In all of the foregoing characterizations the TCuPhM pigments are
stationed around the origin whereas the CuPh pigments appear in
the far blueered zone of the diagram. In fact CuPh was a blue
pigment whereas TCuPh was green. The carboxamide groups
located on the phthalocynanine shifted the color from blue to green.
free phthalocyanine derivatives and
a comparison with conventional
methods of their synthesis. Turkish J Chem 2009;33:123e34.
[18] Lokesh KS, Uma N, Achar BN. The microwave-assisted syntheses and
a conductivity study of a platinum phthalocyanine and its derivatives. Poly-
hedron 2009;28:1022e8.
[19] Shaabani A, Moghaddam RM, Maleki A, Rezayan AH. Microwave assisted
synthesis of metal-free phthalocyanine and metallophthalocyanines. Dyes
Pigm 2007;74:279e82.
4. Conclusions
[20] Pfaff G. Special effect pigments. Vincentz; 2008.
Combination pigments were synthesized by depositing CuPh
and TCuPh pigments onto mica-titania substrate. CuPh pigment
crystallites formed on the mica-titania surface at all temperatures
[21] Noguchi IT, Watanabe OT, inventors; Merck Patent Gesselschaft, assignee.
Flaky colored pigments, methods for their production, and their use in
cosmetic compositions, US Patent 4772331; 1988 Sep 20.
[22] Armanini L, inventor; The Mearl Corp, assignee. Colored micaceous pigments,
studied. The stable b-CuPh form was achieved on the surface of
US Patent 4755229; 1988 Jul 5.
CuPhM pigment at deposition temperatures of 90 ꢀC and 120 ꢀC. On
the other hand, amorphous TCuPh structure was obtained on the
surface of TCuPhM pigment at all temperatures. The resulting
[23] Topuz BB, Gündüz G, Mavis B, Çolak Ü. The effect of tin dioxide (SnO2) on the
anatase-rutile phase transformation of titania (TiO2) in mica-titania pigments
and their use in paint. Dyes Pigm 2011;90:123e8.