XRD Analysis

Test Condition: The XRD profile of nanoclay and various PMMA nanocomposite samples was
done under air at room temperature, using the AXS D8 ADVANCE Fully Automatic Powder X-
ray Diffractometer (Bruker) equipped with a Cu-Kα radiation (λ = 0.15406 nm) and Ni filter. The
patterns were recorded for 2θ range from 1o to 70o with a scan speed of 0.05o sec -1.

XRD is utilized as a valuable tool to characterize the types of the layered structure, i.e.
intercalated and/or exfoliated polymer/clay nanocomposites, because the peak position changes
with the gallery height of the nanoclay. In the case of intercalated nanocomposites, the XRD
peak is seen at a larger d-spacing value than in the clay, whereas in the case of exfoliated
structure, no peak is seen. The d001 spacing is calculated from the peak position using Bragg’s
law: nλ = 2d sin θ, where λ is normally the X-ray wave length (1.5406 Å) and n = 1.
*Wavelength change in nanometer i.e. 0.15406 nm and sinθ will be half as 2θ is mentioned in graph.

Figure 1. depicts the XRD patterns of nanoclay and various PMMA nanocomposites. The basal
spacing (d001) of (001) peak that appears at 2θ value of 4.15o for the nanoclay is determined to be
2.13 nm. For neat PMMA, the diffraction peak appears at 2θ = 13.34o and the large broad hump
originates from the PMMA matrix. It is evident from Figure 2.1 that for the PMMA-5 sample,
the basal spacing (d001) of (001) peak of the clay layers increases to 3.67 nm from 2.13 nm of the
pure nanoclay. A similar range of basal spacing (3.54 nm) is also found for PMMA-5-G sample.
It is noticed that nanoclay layers in the nanocomposites have been intercalated because single
extended polymer chains can penetrate between the silicate layers, and a well-ordered multilayer
morphology results with alternating polymeric and inorganic layers.

Figure 1. XRD patterns of nanoclay, neat PMMA, PMMA-5 and PMMA-5-G nanocomposites
 DSC Analysis

Test Condition: Differential scanning calorimetry (DSC) was performed on a Metler Toledo-1
series to evaluate the glass transition temperature (Tg) of the PMMA nanocomposites. Samples
were heated from 25 to 250 oC at a rate of 10 oC min-1 under nitrogen atmosphere (N2 flow rate
of 50 mL/min). Around 6 mg of extruded pellets were used for DSC analysis.

To investigate the mobility of PMMA chains in terms of its Tg (glass transition temperature) in
the clay layers, DSC study of neat PMMA and the nanocomposites has been carried out and the
results are illustrated in Figure 2. The glass transition temperature is determined at the inflection
point between the onset and the end-set temperatures. DSC thermograms represent the presence
of second order transition corresponding to the Tg of neat PMMA matrix around 109.31 oC.
However, there is no first order transition, which indicates the absence of melting temperature,
thus confirming amorphous characteristics of the matrix polymer. DSC isotherm of PMMA-5
nanocomposite reveals Tg around 110.36 oC. The grafted sample i.e. PMMA-5-G also
demonstrates glass transition temperature around 109.58 oC indicating no appreciable effect of
grafting agent (PMMA-g-MA) on the segmental mobility of the matrix polymer. The Tg of
intercalated polymer nanocomposites is a complicated function of the nature of organic modifier,
weight loading of clay, the mean dominant d001 spacing of the interlayer gallery space and
dispersion and arrangement of the clay stacks in the polymer matrix.

Figure 2. DSC curves of neat PMMA, PMMA-5 and PMMA-5-G nanocomposites

Test Condition: Thermogravimetric analyses (TGA) of the nanocomposites and nanoclay were
carried out on Mettler Toledo thermo gravimetric analyzer, (TGA/SDTA 851® model,
Switzerland). Samples were placed in 900 µl crucible. The samples were heated from room
temperature to 700 oC at a heating rate of 10 oC/min under nitrogen flow of 60 mL/min.

TGA is used to characterize the degradation and thermal stability of the polymer. The dispersion
of clay is known to improve the thermal stability of the polymers. Figure 3 represents the TGA
curves for nanoclay, neat PMMA and PMMA nanocomposites (PMMA-5 and PMMA-5-G). The
TGA graph of nanoclay exhibits that total weight loss of about 30% occurs between 50 to 800
o
C. A small weight loss at temperature <300 oC corresponds to the removal of adsorbed water
present in the nanoclay. The weight loss between 300 and 450 oC is due to the degradation of the
organic modifier present in the clay. There is also decomposition at above 450 oC, which is
correlated with dehydroxylation of aluminosilicate.

The parameters that are important from TGA curves are the onset of degradation, which is
usually taken as the temperature at which 10% degradation occurs, T10%, and the midpoint
temperature of degradation, T50%. From the TGA curves, it is clear that the thermal stability of
both PMMA-5 and PMMA-5-G samples is higher, which is confirmed by shifting of the TGA
curve of PMMA nanocomposites towards right of the TGA curve of neat PMMA. When 10%
weight loss is selected as a point of comparison, the decomposition temperature of neat PMMA,
PMMA-5, and PMMA-5-G is found to be 343.6, 351.0 and 350.6 oC, respectively. The results
demonstrate that the degradation of the nanocomposites takes place at a higher temperature than
that of neat PMMA (7-8 oC higher than that of neat PMMA) in the presence of nanoclay. When
50% weight loss is chosen as a point of reference, the decomposition temperature of the
nanocomposites is found to be 10-11 oC higher than that of neat PMMA. This behavior could be
explained by the presence of barrier effect of nanoclay lamellar layers, which limit the emission
of the produced degradation gases and transmission of heat, therefore resulting in the
improvement in thermal stability of the nanocomposites. These results disclose that the PMMA
nanocomposites exhibit better thermal stability than that of neat PMMA. The increase in the
onset temperature signifies delayed degradation of PMMA nanocomposites.
Figure 3. TGA curves of nanoclay, neat PMMA, PMMA-5 and PMMA-5-G
nanocomposites