Effect of Organoclay Content on Cellulose Acetate Nanocomposites Properties

A. Coloma, F. J. Rodríguez, M. J. Galotto, A. Guarda, and J. E. Bruna

Center for the Development of Nanoscience and Nanotechnology (CEDENNA). Universidad de

Santiago de Chile. Technological Faculty. Science and Food Technology Department. Food
Packaging Laboratory.

INTRODUCTION

The use of plastic packaging has increased in recent years; this has led to excessive levels of
plastic wastes to the environment. So, this problem has been causing concern to the scientific
community to develop eco-friendly materials.1-3 An alternative to face this situation could be
consisted in the use of polymers biodegradable, however, their application is limited due to
problems related to performance (such as brittleness, poor barrier to gases and water vapor),
processing and cost.4.5 So, the incorporation of clay particles or other layered silicates with
nanometer scale in polymers has risen as a alternative to modify the negative properties of
these kind of polymers. In this way, the aim of the present work was evaluated the effect of a
commercial organoclay (Cloisite30B) content on the properties of cellulose acetate
nanocomposites.

The aim of this work was to evaluate the effect of Cloisite 30B content on the physical
properties of cellulose acetate nanocomposites.

EXPERIMENTAL

Cellulose acetates (Mn 30,000 and Mn 50,000) were purchased from Sigma Aldrich Organically
modified montmorillonite clay Cloisite® 30B was purchased from Southern Clay Products, Inc.
Triethyl citrate (99%) was purchased from SAFC Supply Solutions.

The nanocomposites were prepared according to a procedure previous reported.6 X-ray

Diffraction (XRD) was performed in a Siemens diffractometer D5000 (30 kV and 40 mA) using
CuK ( = 1.54 A) radiation at room temperature in a 2θ range from 2 to 40° to 0.02°/sec and
the interlayer distances were calculated according to Bragg's equation.7 Differential Scanning
Calorimetry was performed on a Mettler DSC-822e calorimeter, the samples were heated from
20 to 300ºC at a rate 10°C/min. Finally, the Oxygen Transmission Rate (OTR) was measured by
oxygen permeation analyzer Mocon Ox-Tran® MS2/20 at 23°C and 0% relative humidity until
the oxygen transfer rate reached equilibrium.

RESULTS AND DISCUSSION

Table 1 shows the results of characterization by X-ray diffraction and DSC of nanocomposites.
It can be observed that an increase of the content of Cloisite 30B in the nanocomposite
produced an increase of the interlayer distance in the organoclay. So, to 10 wt. %, the
interlayer space increased to 2.23 nm and 2.25 nm for CA low molecular weight and high
molecular weight respectively. This behavior is according with the intercalation of cellulose
acetate inside the clay structure which was most important to nanocomposites with high
molecular weight.

Table 1. Results of characterization of nanocompositos by XRD and DSC

Molecular Organoclay Interlayer

2 Tgb Tmb Hfb Xcc
Weight content distance
(º) (ºC) (ºC) (J/g) (%)
CA (wt. %) (nm)

30,000 0.0 ns --- 134 175 0.68 1.16

30,000 2.5 4.00 2.21 123 156 0.53 0.90

30,000 5.0 3.98 2.22 117 156 0.47 0.80

30,000 7.5 3.92 2.25 110 151 0.39 0.66

30,000 10.0 3.94 2.23 101 136 0.30 0.51

50,000 0.0 ns --- 124 160 0.62 1.05

50,000 2.5 4.20 2.10 116 156 0.53 0.90

50,000 5.0 4.18 2.11 113 154 0.45 0.77

50,000 7.5 4.08 2.16 110 152 0.37 0.63

50,000 10.0 3.92 2.25 110 150 0.28 0.48

a
Calculated using Bragg`s Laws; b Determined from second scan; c Calculated from Hf
6
100% =58.8 J/G. ns: no signal

2200

2000 CA 30,000
1800
CA 50,000

1600
OTR (cm /m day)

1400
2

1200
3

1000

800

600

400

200
0,0 2,5 5,0 7,5 10,0
Cloisite 30B (wt. %)

Figure 1. Effect of organoclay content in the oxygen permeability on cellulose nanocomposites

Regarding to DSC analysis an important decrease of Tg, Tm and Hf values according to
increase of Cloiste30B content was observed. This effect could be explained by the presence
of organic component with alcohol groups (2-hidroxyethyl) derived from commercial
organoclay inside of polymer structure which could be acting as a plasticizer agent decreasing
the glass transition temperature and hindering the polymer crystallization.8 Finally, the
nanocomposites films were analyzed by OTR (Figure 1). The OTR parameter decreased with
increasing of Cloisite 30B content to all cellulose acetate nanocomposites. This reduction can
be explained due to the path tortuous generation when layered silicates are dispersed in the
polymer structure. So, a high content of layered silicates incorporates inside the polymer
matrix favors a mayor generation of tortuous path which favors a reduction on the oxygen
permeability.

CONCLUSIONS

All nanocomposites elaborated showed the intercalation of cellulose acetate inside the clay
structure. The intercalation grade was affected by organoclay content and molecular weight of
CA. Plasticizer effect of organic component of commercial organoclay was observed on all
nanocomposites. Important changes on the oxygen permeability of nanocomposites were
evidenced with the organoclay composition and molecular weight of cellulose derivative.

ACKNOWLEDGMENTS

The authors thank to Comisión Nacional de Investigación Científica y Tecnológica, CONICYT, for
the financial support from Programa Bicentenario de Ciencia y Tecnología (Project PDA-22),
Programa de Financiamiento Basal para Centros Científicos y Tecnológicos de Excelencia
(Project FB0807) and Programa FONDECYT de Iniciación (Project 11100389). To Departamento
de Investigaciones Científicas y Tecnológicas, Universidad de Santiago de Chile, DICYT-USACH
(Project 080971RM). A. Coloma thanks to OEA for Doctoral Scholarship.

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