Synthesis and Characterization of

Multifunctional Inorganic-organic
Nano Composites Involving Dye
Intercalated Alumino Silicates

Annual Session of the Indian Ceramic Society

Visakhapatnam

P. Krishna Pillai, P. Perumal, P. Shajesh, K.A. Manju Mol, V.S.

Smitha, C. Pavithran and K.G.K. Warrier*

Materials & Minerals Division,

Regional Research Laboratory (CSIR),
Trivandrum695 019 India
 Overvi
ew

Large quantities of pigments are used to impart colour to

various products based on plastics, polymer, paints glass and
ceramics
Mostly the pigments have their origin from heavy metals and
compounds, which are environmentally hazardous and non-
ecofriendly
One of the approaches to eco-friendly pigments is to
intercalate organic dyes into inorganic layered and porous
substrates, such as naturally occurring alumino silicates
The present work deals with the intercalation of methylene
blue into montmorillonite, modified with different alkyl
ammoniums as exchangeable cations
 Eco Friendly Nano Pigments

DYE
Molecules

Dye Intercalated layered clay

blended with polyehylene and
shaped. to sheet
Schematic Description of Metal Oxide
Pillaring
 Preparation of Intercalated Nano
Pigments

30gm Bentonite
3L Water Mono ion
exchange using
NH4OH, stirred
NH4+ Bentonite for 6H
Methylene blue 2L Water
(.1%) 40 ml
6H stirring Methylene Blue
Intercalated
Bentonite
pH 3.4-3.6
Washed &
Dried at 70C
 Various Approaches for the Synthesis
of Intercalated Inorganic Organic
Nano Pigments

Intercalated Studied the effect of various methods: stirring,

Nano refluxing, ultrasonication on effect of exchange
Pigments molecule before intercalation of methylene blue

Methods of preparation d(001) before intercalation d(001) after intercalation

A0 A0

Stirring 12.63 15.13 (6hr)

Refluxing 12.63 13.88 (6 hr)
Ultrasonication 12.63 14.85 (1 hr)
12.85 (4 hr)
 Stability to UV Exposure

Unadsorbed MB Intercalated MB

Time (H) Decomposition of dye Decomposition in intercalated clay

(%) (%)
0 0 0
1 13.06 0
2 39.62 0
3 45.49 0
4 56.27 0.13
 Stability to UV Exposure

1.0

0.15 MB 0 time 0.9

+ 0Hr
30m B+MB(NH4 )
0.8 2Hrs
1h 15m 4Hrs
0.12
0.7 8Hrs
0.6
0.09
0.5
Abs.

Abs.
0.06 0.4

0.3
0.03
0.2

0.1
0.00
0.0

400 500 600 700 800 -0.1

400 500 600 700 800
Wavelength (nm)
Wavelength,nm
 Thermal Stability

MB Intercalated MB

TG & DTA
 (a) 30 mts ultrasonicated
sample

(b) 4 h ultrasonicated

Ultrasonication decreases the Si-O-Si stretching absorption

The absence of H aggregates for the 4 h ultrasonicated sample
from the UV absorption and lower d spacing of 100 plane for the
same sample suggests the growing of Si tetrahedras towards the
interlayer space decreasing the inter layer space
 Conclusions

Organic dye intercalated layered silicates show

promise as eco friendly nano pigments due to low
concentration of organics and the host material
being natural
The intercalated nano pigments show high stability
to UV light and hence could be an additive to
polymers for increasing durability
Organic hybrid pigments can partially substitute
the use of difficult to dispose heavy metal oxide
pigments
Intercalated pigments can be uniformly dispersed
in polymer matrices and develop uv stable uniform