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Applied Clay Science 107 (2015) 205212

Contents lists available at ScienceDirect

Applied Clay Science


journal homepage: www.elsevier.com/locate/clay

Research paper

Development of transition metal oxidekaolin composite pigments for


potential application in paint systems
Swagata Roy a, Subrata Kar a, Biswajoy Bagchi b, S. Das a,
a
Department of Physics, Jadavpur University, Kolkata 700032, India
b
Fuel Cell and Battery Division, Central Glass and Ceramic Research Institute, Kolkata 700032, India

a r t i c l e i n f o a b s t r a c t

Article history: The present work deals with a simplied process for synthesizing metal oxides of Cu(II), Ni(II), Cr(III) and Fe(III)
Received 26 September 2014 imbibed kaolin pigments and characterizing those samples using X-ray diffraction, Fourier transform infrared
Received in revised form 7 January 2015 spectroscopy, FESEM and EDS in addition to the visual classication by color. Furthermore, PEG analysis and
Accepted 30 January 2015
antimicrobial potency of these samples were investigated thoroughly which conferred positive impact depicting
Available online 12 February 2015
the fact that these metal oxides incorporated kaolin composites can serve as a good and promising ceramic
Keywords:
pigment material in paint systems. Due to easy availability of kaolin and involvement of low temperature, the
Kaolin production cost of these synthesized pigments is highly reduced which can be an added advantage to the paint
Metal oxide composite industry.
Ceramic pigment 2015 Elsevier B.V. All rights reserved.
Antimicrobial potency
PEG analysis

1. Introduction research is to study the plausibility of synthesizing ceramic pigments


using natural mineral raw material which could make the pigments
The recent era has witnessed the blooming rise in the development of cost-effective and available in all sectors. Inorganic pigments using
tailored materials with multifunctional properties. It is well known that metal oxides in ceramic and plastic industry have attracted attention
the transitional metallic oxides are chromophores and hence are a source at the present time. In general, inorganic pigments are superior to
of pigments (Pishch et al., 2011). The transitional metals like Cu, Ni, Cr organic ones in heat and light permanency, weather resistance and
and Fe have unlled electronic shells and possess high polarizability. low cost. Few works related to ceramic pigments using silica gel as the
Generally the formation of the complex ions of these metals due to the precursor have been reported earlier (Krysztafkiewicz et al., 2003;
incorporation of oxygen, shifts the absorption band in the visible region Pishch et al., 2011). The pigments based on the silica are popular
of the electromagnetic spectrum and is accountable for obtaining a among ceramic pigments. Besides silicates, aluminosilicates can also
wide range of colored pigments. However some of these materials also be used as another silica source. Kaolin, an aluminosilicate material
possess antimicrobial properties which when incorporated into the can be used as the silica source to synthesize ceramic pigments.
paint systems act as agents to control the growth of microbes. It is a Kaolin is a natural light colored clay occurring worldwide in large
matter of concern that majority of the harmful microorganisms have deposits and hence is an inexpensive raw material. It has good
developed a gradual resistance to most of the conventional antimicrobial dispersibility in water based system, good opacity, gloss and brush
agents. This has led researchers towards engineered nanomaterials as a ability. It is used as a precursor in paper industry. Pigments based
way out to the problem. Recent studies have been reported about the on kaolin can be used in colored paper production, as colored pigment
antimicrobial effects of various materials (Moralesa et al., 2003). The or extender in paint industry. In decorative paints it will be a good
development of various new microbe deterrents is an ever evolving ingredient. Kaolin, with the chemical composition Al2Si2O5(OH)4 is
expertise. In this context the oxides of metals like copper, nickel, iron, available in pure form and in very ne particles. It is a layered silicate
chromium, etc. in their nano or micro regime prove to be ideal antimicro- with one tetrahedral sheet linked through oxygen atoms to one octahe-
bials (Pang et al., 2009; El-Nahhal et al., 2013; Hans et al., 2013; Prodan dral sheet of alumina. It has a special water retentive property. These
et al., 2013; Swain et al., 2014). particles slide over each other to form plastic clay like mass. Other
Paints have been manufactured since time immemorial but until special features include its good thermal resistivity, good electrical insu-
recently they were highly expensive. Hence, a promising direction in lation and non-abrasiveness. It is used in paint as it is chemically inert
over a wide pH range, has a high covering power, is a good plasticizer,
Corresponding author. Tel.: +91 9433091337. provides smoother surfaces, and gives more attractive nish and good
E-mail address: sdasphysics@gmail.com (S. Das). dimensional stability. In addition, kaolin is also a versatile extender

http://dx.doi.org/10.1016/j.clay.2015.01.029
0169-1317/ 2015 Elsevier B.V. All rights reserved.
206 S. Roy et al. / Applied Clay Science 107 (2015) 205212

Table 1 pigment which apart from giving good performance in paint lms, also
Kaolinmetal oxide composites and their respective colors. gives ample opportunity for value addition by physical, structural and
Kaolinmetal oxide composites Color chemical modication with enhanced performance (Slepetys and
KaolinCuO Black
Cleland, 1993; El-Sabbagh et al., 2012).
KaolinNiO Gray The present work focuses on the low temperature preparation of
KaolinCr2O3 Green kaolinmetal oxide ceramic pigment from oxides of Cu(II), Ni(II), Cr(III)
KaolinFe2O3 Red and Fe(III) [KCuO, KNiO, KCr2O3, KFe2O3 samples respectively] in a
cost-effective way. The synthesized composite samples of metal oxide
embedded in kaolin matrix serve a two-fold purpose as a pigment and

Fig. 1. (a): XRD pattern of puried kaolin powder sample. (b): XRD patterns of kaolinmetal oxide composite samples with various mass ratios of oxides from 0 to 30%.
S. Roy et al. / Applied Clay Science 107 (2015) 205212 207

Table 2
XRD data analysis of kaolinmetal oxide composite pigment samples.

Sl. no. Metal oxide in kaolin 2 values (degree) Corresponding hkl planes JCPDS no. Average particle size (Dhkl) in nm

1. CuO 35.5, 68.1 (002/111), (220) 80-1917 D002 = 21.7


2. NiO 37.3, 43.3, 62.9 (111), (200), (220) 78-0643 D200 = 20.0
3. Cr2O3 24.5, 33.6, 36.2, 54.9 (012), (104), (110), (116) 85-0869 D104 = 58.2
4. Fe2O3 33.2, 35.6, 54.1, 64 (104), (110), (116), (300) 86-0550 D104 = 51.8

a suitable antibacterial agent thus retarding any bacterial growth on the content. Copper oxide (CuO), nickel oxide (NiO), chromium oxide
surfaces where the pigment is applied. (Cr2O3), ferric oxide (Fe2O3), polyethylene glycol 6000, and NaCl were
all purchased from Merck, Germany. Beef extract, peptone, yeast extract,
2. Experimental and agar were obtained from Himedia Pvt. Ltd., India.

2.1. Materials 2.2. Experimental procedure

Kaolin samples were collected from Rajmahal Hills (RH) in Jharkhand, The as obtained kaolin was nely mortared and stirred in ample
India. The Rajmahal clay had a faint light brown color with higher quartz quantity of de-ionized water for 30 min. Then it was centrifuged

Fig. 2. (a): FTIR spectra of puried kaolin powder sample. (b): FTIR spectra of kaolinmetal oxide composite samples with various mass ratios of metal oxides from 3% to 30%.
208 S. Roy et al. / Applied Clay Science 107 (2015) 205212

Fig. 3. (a) FESEM image (left), elemental mapping image (middle) and EDS (right) of KCuO composite (30%). (b) FESEM image (left), elemental mapping image (middle) and EDS (right)
of KNiO composite (30%). (c) FESEM image (left), elemental mapping image (middle) and EDS (right) of KCr2O3 composite (30%). (d) FESEM image (left), elemental mapping image
(middle) and EDS (right) of KFe2O3 composite (30%).

(12,000 rpm, 10 min) several times to wash out the unwanted impuri- 2.3.3. Field emission scanning electron microscopy (FESEM) and energy
ties and dried in hot-air oven to obtain the pure clay. Metal oxides viz. dispersive X-ray spectroscopy (EDS)
CuO, NiO, Cr2O3 and Fe2O3 with various mass percentages i.e. 3%, 5%, The surface morphology, chemical analysis and imaging/mapping of
10%, and 30% of each respective metal were measured so as to prepare the prepared kaolinmetal oxide composite samples were featured by
1 g of sample. Briey, kaolin was added in de-ionized water and stirred FESEM (INSPECT F50, The Netherlands). Powder samples were nely
for 60 min followed by the addition of the measured metal oxides. They
were allowed to stir overnight for uniform mixing. After that the disper-
sion was centrifuged at 12,000 rpm for 10 min and washed several Table 3
times with deionized water to remove the free metal oxides. The mate- Representation of mass percentages of elements in the composites obtained from EDS
study.
rial was dried at 80 C. The dried samples were mortared well for further
characterizations. Sample Element Atom % Weight %

KaolinCuO Oxygen 48.13 62.58


2.3. Material characterization Aluminum 24.66 19.02
Silicon 22.99 17.03
2.3.1. X-ray diffraction (XRD) Copper 4.22 1.38
KaolinNiO Oxygen 46.46 62.42
Crystallization behavior of the samples was examined with the aid of Aluminum 22.55 17.96
X-ray diffraction technique (Model-D8, Bruker AXS Inc., Madison, WI) Silicon 20.71 15.85
operating at 40 kV with scan speed of 0.1 s/step from 10 to 80 2 Nickel 10.28 3.77
values. KaolinCr2O3 Oxygen 48.09 63.26
Aluminum 21.99 17.15
Silicon 21.73 16.28
2.3.2. Fourier transform infrared spectroscopy (FTIR) Chromium 8.19 3.31
The IR spectra of the prepared samples including kaolin were ana- KaolinFe2O3 Oxygen 44.52 61.78
lyzed using the Fourier transform infrared spectrometer (FTIR-8400S, Aluminum 20.09 16.54
Shimadzu). 10 mg of sample was thoroughly mixed with 1 g of KBr Silicon 19.35 15.30
Iron 16.04 6.38
and nely mortared for the study.
S. Roy et al. / Applied Clay Science 107 (2015) 205212 209

mortared and were carefully spread on a carbon tape and gold-coated The presence of metallic oxides was conrmed by matching with the
before FESEM analysis was carried out. An analytical technique, EDS, corresponding JCPDS cards in Table 2. The average particle size of pris-
was carried out for the elemental analysis or chemical characterization tine kaolin and metal oxide composites was calculated by employing
of the synthesized samples. Mapping or imaging of the thin section of the DebyeScherrer formula Dhkl = k / Cos, where is the full
the synthesized samples was performed in order to get an image of width at half maximum of the associated crystallographic plane, k is a
the chemical composition of all the samples. constant related to the shape of the particle, is the incident X-ray
wavelength and is the Bragg's angle respectively. Using this method
2.3.4. Treatment with polyethylene glycol (PEG) and consequential analysis the calculated value of the average particle size of the pure kaolin was
0.2 g of polyethylene glycol (PEG) was taken in 20 ml of distilled 49.1 nm which corresponds to the (001) crystallographic plane. The
water and 1 g of kaolinmetal oxide composite samples was added to respective particle sizes of metal-oxides incorporated in kaolin are
the former and stirred at 50 C till slurry was formed. Then the slurry represented in Table 2.
was drop casted on a glass plate as well as on an alumina plate and
kept in a hot-air oven at 100 C for complete evaporation of water. 3.2. FTIR analysis

FTIR study was implemented for all the samples of kaolin as well as
2.3.5. Antimicrobial assay
the kaolinmetal oxide composites. The FTIR spectra of the kaolin and of
The antibacterial activities of the synthesized pigments were per-
the composite samples are shown in Fig. 2(a) & (b) respectively.
formed using gram-negative Escherichia coli (MTCC-1652) and gram-
For kaolin the spectra were taken in the wavelength range of
positive Staphylococcus aureus (MTCC-96). Briey from overnight
400 cm1 to 4000 cm1 whereas in the case of metal oxide composites,
grown bacterial cultures, a volume of culture representing ~ 105 cells
the wavelength range from 400 cm1 to 2000 cm1 was chosen. For all
was inoculated in a fresh nutrient broth (0.5% peptone, 0.1% beef
the samples there is a broad band around the region of 3420 cm 1
extract, 0.2% yeast extract, 0.5% NaCl, pH 7). The inoculated broths
which is ascribed to the stretching modes of surface O\H groups. All
were treated with 30 mg of each 10% and 30% samples. An inoculated
the prepared samples absorb moisture from the air and the presence
but untreated broth served as control. The cultures were then incubated
of water molecules gives rise to the broad band in this region. The
at 37 C. After the period the cultures were plated in a nutrient agar
signals at 3620 cm1 and 3710 cm1 are attributed to the inner hydroxyl
plate (1.8% agar) and incubated overnight at 37 C.
O\H stretching and in-phase stretching of the inner surface O\H groups
respectively. Signals near 3670 cm1 and 3652 cm1 are as a result of the
3. Results and discussions anti-phase stretching modes of the inner surface O\H groups. The anti-
symmetric stretching of Si\O bonds represents the absorption near
The kaolin clay sample and all the kaolinmetal oxide composites 1032 cm1. The band at 1090 cm1 represents the symmetric stretch
were analyzed. Addition of calculated mass percentages of metal oxides of Si\O bonds. Both these bands are a conrmatory sign of the presence
imparts color to the composite samples which is desirable in the appli- of kaolin (Mon et al., 2011). The FTIR spectra of kaolin mixed with various
cation of these composite pigment materials in paint systems. Kaolin mass percentages of metal oxide incorporated in the kaolin matrix are
metal oxide composite pigments synthesized from CuO, NiO, Cr2O3 demonstrated in Fig. 2(b). Generally the inter-atomic vibrations from
and Fe2O3 yield vibrant colors (Table 1). the metal oxides arise below 1000 cm1. For KCuO composite the
These colors can be quite alluring in the paint industry. The color of peak at 509 cm1 is attributed to the framework vibration of CuO (Xia
the pigment samples intensied with the increase in percentages of the and Yang, 2012). For KNiO sample, the broad absorption band in the
oxides in kaolin. The melting points of copper oxide, nickel oxide, region of 600700 cm1 is assigned to the Ni\O stretching vibration
chromium oxide and iron oxide are 1201 C, 1955 C, 2435 C and (Qiao et al., 2009). Absorption bands below 1000 cm1 due to inter-
1565 C respectively, hence these oxides are stable at high temperatures atomic vibrations are also present in the case of chromium oxide and
providing a classical possibility for successful employment of these ferric oxide counterparts. In the case of KCr2O3 there are vibrational
synthesized ceramic pigments in the paint systems. The samples are bands below 1000 cm1 for the associated Cr\O stretching modes
further characterized as follows. (Farzaneh and Naja, 2011). For KFe2O3 composite sample the bands
in the region of 500 cm1 can be attributed to the Fe3+O2 bond
3.1. X-ray diffraction in the FeO6 octahedron and FeO4 tetrahedrons. Besides the absorption
band at 1635 cm1 for all the samples is attributed to the H\O\H
X-ray study demonstrates the powder XRD patterns of pre-treated bending vibrational modes which may be due to the adsorption of
kaolin powder and also kaolin mixed with various mass ratios of the water by the samples (Chen et al., 2012).
metal oxides (Fig. 1). The reection of kaolin and that of the correspond-
ing metallic oxides is represented. There is a general trend of increase in 3.3. SEM and EDS analysis
reection intensity of the metal oxides as their concentration increases.
The metal oxides thus have been successfully embedded in the kaolin Scanning electron microscopy, along with energy dispersive spectros-
matrix without change in any chemical composition. copy was used in this work to estimate the particle size, shape or
Some of the prominent reections associated with the 2 values of morphology and the distribution of various components in the composite
12.34, 20.34, 24.88, 26.40, 35.99, 38.50, 55.02 and 62.36 (in degree) sample. The presence of various elements was quantitatively estimated
having the corresponding hkl miller planes (001), (110), (002), (111), by EDS analysis.
(200), (131), (240) and (331) matches well with the main reections In the structure of kaolin there are two sublayers. The AlO6 sublayer
of kaolin (Al2Si2O5(OH)4) (JCPDS Card No. 14-0164) (Zhang et al., consists of octahedral coordination of Al and water (hydroxyl groups).
2014). However in this natural raw clay mineral there were some reec- There is another sublayer of SiO4 consisting of tetrahedrally coordinated
tions of crystalline quartz. The reections for 2 values like 20.86, 26.64, Si. The sublayers are held together by Al\O\Si bonds. These interatom-
36.54, 50.14, 59.96 and 68.14 (in degree) for the respective hkl planes ic layers are destroyed due to geological activities and the unsaturated
(100), (101), (110), (112), (211) and (203) agree well with the standard oxygen atoms are exposed to the surface due to the broken bonds of
powder diffraction data for quartz (SiO2) (JCPDS Card No. 46-1045). The Al\O\Si, Al\O\Al and Si\O\Si (Zhang et al., 2014). The loose particle
reections in the region of 1924 and 3440 are very close to each aggregates often form hexagonal platelet like structures. The platelets
other. For the ease of indexing, these regions are separately represented come in contact with each other and they give the mix ow ability for
in the insets of Fig. 1(a). molding of complex shapes. This property of kaolin is utilized as a
210 S. Roy et al. / Applied Clay Science 107 (2015) 205212
S. Roy et al. / Applied Clay Science 107 (2015) 205212 211

Fig. 5. (a): Agar plate of E. coli treated with (a) 10% KCuO composite, (b) 30% KCuO composite, (c) 10% KNiO composite, (d) 30% KNiO composite, (e) 10% KCr2O3 composite, (f) 30%
KCr2O3 composite, (g) 10% KFe2O3 composite, and (h) 30% KFe2O3 composite. (b): Agar plate of S. aureus treated with (a) 10% KCuO composite, (b) 30% KCuO composite, (c) 10%
KNiO composite, (d) 30% KNiO composite, (e) 10% KCr2O3 composite, (f) 30% KCr2O3 composite, (g) 10% KFe2O3 composite, and (h) 30% KFe2O3 composite.

versatile extender pigment. The SEM images of the synthesized pigment composite samples of highest percentage. The elemental mapping in
samples of kaolin containing 30% by mass of CuO, NiO, Cr2O3 and Fe2O3 color image with the energy dispersive spectra was also shown in
respectively were taken under the same magnication. Fig. 3. The mass and atomic percentages of the various elements are pre-
A general plate or ake like morphology is obtained for all the sented in Table 3. It depicts that the incorporated metal oxides have a
samples which are characteristic of kaolin particles (cf. Fig. 3). The signicant percentage in the kaolinmetal oxide composite matrix.
particles represent microscopic hexagonal plates and cluster of plates
agglomerated into compact, claylike masses (Ahmed and El-Sabbagh, 3.4. PEG analysis
2014). However there were no observable morphologies of the metal
oxides in the composites. For all the samples the particle size ranges For all kinds of paints it is necessary that the quality of the surface
from 100 nm to 500 nm. All the EDS measurements were done on the (after the application of paint) should be smooth, long lasting and

Fig. 4. (a): PEG analysis of composite sample (30% of metal oxide) on glass substrate: (a) KCuO, (b) KNiO, (c) KCr2O3, and (d) KFe2O3. (b): PEG analysis of composite sample (30% of
metal oxide) on alumina substrate: (a) KCuO, (b) KNiO, (c) KCr2O3, and (d) KFe2O3.
212 S. Roy et al. / Applied Clay Science 107 (2015) 205212

crack free. It is well-known that a suitable binder has a considerable Acknowledgments


effect on the densication of the ceramic pigment. The nature of the
used binder has a signicant effect on the mechanical properties of One of the authors (S.R.) wishes to thank the University Grants
the samples. They give plasticity, uidity and provide enough strength Commission (UGC F.42-772/2013(SR)), Govt. of India for providing fel-
to avoid any cracking or distortion. Using polyethylene glycol (PEG lowship during the execution of this work. The other authors also wish
6000) gives the pigment material a higher tensile strength. Also as the to acknowledge the Department of Science and Technology, Govt. of
binder content increases, granules become hard and difcult to distort India (DST SR/NM/NS 103-2010) for nancial support.
which enhances the pigment quality and gives a superior and smooth
nish. The presence of PEG thus alters the mechanical properties of References
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