Article

pubs.acs.org/IECR

Degradation Behavior of Polypropylene−Organically Modified Clay

Nanocomposites
K. J. Singala,†,‡ A. A. Mungray,*,† and A. K. Mungray*,†
†
Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat 395007, Gujarat, India
‡
Reliance Industries Limited, Hazira Manufacturing Division, Surat 394510, Gujarat, India

ABSTRACT: The degradation mechanism of polypropylene (PP)−clay nanocomposites is investigated in the present study.
The PP−clay nanocomposites are prepared through a solution process with 4 and 8 wt % incorporation of nanoclay in a polymer
matrix. Nanoclay with two types of organic modifications (25−30 wt % methyl dihydroxyethyl hydrogenated tallow ammonium
(TA) and 25−30 wt % octadecylamine (OA)) is used with isotactic PP, atactic PP, and ethylene propylene copolymer with ∼20
wt % rubber. Characterization of nanocomposites is done through X-ray diffraction (XRD) analysis while melting and
crystallization behavior is studied through differential scanning calorimetry (DSC). XRD and DSC analysis shows formation of
intercalated type nanocomposites with improved barrier properties. Degradation behavior of nanocomposites is studied through
thermogravimetric analysis (TGA). Weight loss curves are further analyzed through the Friedman technique to find the rate of
degradation. Nanoclay incorporation increases the lifetime of nanocomposites, calculated using an equation derived by Toop
[IEEE Trans. Electr. Insul. 1971, 6, 2−14]. The peak rate of degradation in nanocomposites with isotactic homo PP and ethylene
propylene copolymer is found to increase up to 1.5 times. Atactic homo PP and its nanocomposites show only a marginal
improvement in properties as well as degradation rate. It is also concluded that the rate of degradation increased with clay loading
due to increase in residual impurity.

■ INTRODUCTION
Polypropylene (PP) and polyethylene (PE) are the most widely
used commodity polymers. PP has an advantage over PE due to
its lower bulk density i.e. lower weight to mass ratio;1
moreover, its properties can be altered by altering the side
chain methyl group in the polymer chain.2 Also, incorporation
of a third component such as glass fiber, mica, clay, etc.3
improves the properties of polymer. Montmorillonite (MMT)
type layered silicate clay is now being widely used in
preparation of PP−clay nanocomposites.3−6 The wide usage
is due to its unique properties such as large surface area to
volume ratio, high interfacial reactivity, nano-sized layered
structure, etc.7−10 Nanoclay can be used without any
modification11 or can be organically modified with a suitable
modifier such as octadecylamine7 or stearylammonium8−10 to
reduce surface tension. The use of unmodified clay is limited to
hydrophilic polymers such as polyethylene oxide and polyvinyl
alcohol. Organic modification is done to reduce hydrophobicity
and to increase the interlayer spacing of clay layers.12
Intercalated and exfoliated types of nanocomposites are formed
when PP and nanoclay are mixed. The intercalation type of
nanocomposite is said to be formed when there is partial
retention of the layered structure of nanoclay in a nano-
composite. Exfoliation is said to be formed when the layered
structure of the nanoclay is completely destroyed, and
individual layers are uniformly dispersed in the polymer
matrix.13
Different processes can be adopted for preparation of
polymer clay nanocomposites i.e., in-situ polymerization,
solution intercalation, and simple melt mixing. A melt mixing
process was discovered by Vaia et al.14 where nanoclay and
polymer are mixed in a melt extruder. The extent of mixing
depends on the type and number of screws used in the
extruder. This is the most economical process, as it does not
involve any solvent. This process is also industrially accepted, as
all the manufacturers employ melt extruders for palletization of
resin. Hence, nanocomposites can be prepared without
hardware modification. An in-situ polymerization15,16 process
was first employed for the synthesis of polyamide 6
nanocomposites by the Toyota research group. In this process
polymer formation takes place between the silicate layers of
nanoclay giving a highly exfoliated nanocomposite.5 But for a
PP−clay nanocomposite, the in-situ polymerization process is
less popular as nanoclay tends to deactivate the catalyst, which
is used for propylene polymerization. In the solution blending/
intercalation process, nanoclay is dispersed in suitable solvent.
Polymer is also dissolved in the same solvent in a separate
vessel. Then slowly, these two solutions are mixed under
predefined temperature, pressure, and mixing conditions. In
this process, polymer chains are slowly adsorbed in between the
clay layers. The residual solvent is evaporated to get the
nanocomposites.
Nanoclay, due to its versatile properties such as large surface
area and layered structure, gives better mechanical, fire
resistant, and barrier properties to nanocomposites.7−10,17,18
This is achieved with minimum clay loading as low as 5 wt %.
Lower clay loading also helps in maintaining optical clarity in
the final product. Silicates also act as nucleating agents19,20
improving crystallization kinetics. It also contributes to better
Received: March 22, 2012
Revised: July 5, 2012
Accepted: July 17, 2012
Published: July 25, 2012

© 2012 American Chemical Society 10557 dx.doi.org/10.1021/ie3007616 | Ind. Eng. Chem. Res. 2012, 51, 10557−10564
Industrial & Engineering Chemistry Research Article

thermal stability imparted due to improved barrier properties
toward oxygen and other volatiles.
With improved properties, the life of the polymer will also
increase. Almost all synthetic polymers are nonbiodegradable
and consume huge amount of energy in recycling and
reprocessing. Hence, an efficient mechanism needs to be
developed by which the usable life of polymer increases but
degradation period becomes shorter. In this paper, an attempt
is made to demonstrate the degradation behavior of PP−clay
nanocomposites prepared with nanoclay having two different
types of organic modifications vis-à-vis its virgin counterpart.
all PP is dissolved. A 0.16 g portion of nanoclay
(Montmorillonite (MMT) with 25−30 wt % TA) is
added in the solution and further maintained at the same
temperature with constant stirring for 120 min (the
nanoclay is sonicated in TCB for 12 h prior to use in
experimentation). The solution is cooled to room
temperature to precipitate resultant nanocomposites.
Further, the nanocomposites are washed with n-hexane
and dried to remove traces of solvent.
2. NC−iH2−TA: The process as described in preparation
of NC−iH1−TA is repeated with 0.32 g nanoclay instead

■ MATERIALS AND METHODS

Material. Commercial polypropylene (homo) having 3.0
of 0.16 g.
3. NC−aH1−TA: The process as described in preparation
of NC−iH1−TA is repeated with 4 g atactic homo PP
MFR is dissolved in stabilized xylene at 160 °C. The solution is instead of isotactic homo PP.
cooled to get precipitates of isotactic homo PP. The remaining 4. NC−aH2−TA: The process of preparation of NC−
solvent is then evaporated to get atactic PP. Ethylene propylene aH1−TA is repeated with 0.32 g nanoclay instead of 0.16
copolymer with 20% (wt) rubber content is used as received g.
from the commercial plant (Reliance Ind. Ltd.). MMT, 25−30 5. NC−iC1−TA: The process as described in preparation
wt % octadecylamine (OA), and MMT, 25−30 wt % methyl of NC−iH1−TA is repeated with 4 g ethylene−
dihydroxyethyl hydrogenated tallow ammonium (TA) (Aldrich propylene copolymer instead of isotactic homo PP.
Chem. Co., USA), are used as received. Trichloro benzene 6. NC−iC2−TA: The process of preparation of NC−iC1−
(Aldrich Chem. Co., USA) and n-hexane (Labort, India) are TA is repeated with 0.32 g nanoclay instead of 0.16 g.
used after distillation. All the experiments are carried out under The procedure described above in 1−6 is followed except
a high purity nitrogen atmosphere. MMT with 25−30 wt % OA is used for the preparation of
Nanocomposite Preparation. Polypropylene is dissolved nanocomposites NC−iH1−OA, NC−iH2−OA, NC−aH1−
in trichloro benzene (TCB). In the prepared PP solution, OA, NC−aH2−OA, NC−iC1−OA, and NC−iC2−OA
nanoclay is added under constant stirring at the same (Table 1).
temperature and maintained for a fixed time interval. The Characterization. X-ray diffraction (XRD) measurements
nanocomposites thus formed are separated through precip- are carried on Bruker AXS, D8 Advance X-ray diffractometer.
itation, cooling, washing, and drying.21,22 Three types of PP are The composite sample placed on the zero background, X-ray
used in preparing nanocomposites, namely atactic homo PP, transparent sample holder. The samples then transferred to
isotactic homo PP, and ethylene propylene copolymer. instrument. The step size in XRD measurements is 0.02° and
Nanocomposites with varying amount of clay loading are also the time per step of 12 s. Component analysis is performed
prepared and studied. using TOPAS v3.0 software by Bruker AXS. The melting points
A total of twelve types of nanocomposites (NC) are prepared of nanocomposites measured by differential scanning calorim-
(Table 1) with three different types of polypropylene at 4% etry (DSC) with a Perkin-Elmer DSC-7 at a heating rate of 10
(wt) and 8% (wt) clay loading and two types of organic °C·min−1 from 25 to 230 °C (with a hold for 3 min at 230 °C),
modifiers of clay (OA and TA) as per procedure21 given below; cooling rate of 10 °C·min−1 from 230 to 25 °C, and again
1. NC−iH1−TA: In a 250 mL capacity round-bottom flask, heating from 25 to 230 °C at 10 °C·min−1. The thermal
4 g isotactic homo PP is added in 100 mL TCB. The stability of nanocomposites is analyzed by thermogravimetric
solution is heated to 160 °C under constant stirring until analyzer (TGA) with a Perkin-Elmer TGA-7 at heating rate of
20 °C·min−1 from 50 to 700 °C under oxidative conditions.
Table 1. PP−Clay Nanocomposites with 4 and 8 wt % Clay
Loading in Atactic Homo PP, Isotactic Homo PP, and
Ethylene−Propylene Copolymer with Two Different
■ RESULTS AND DISCUSSION
Preparation of Polypropylene Clay Nanocomposites.
Organic Modifications in Nanoclay XRD is used to determine the extent of mixing of nanoclay in a
polymer matrix. Figure 1a shows the characteristic peak of clay
nanoclay charged polymer nanoclay in polymer and nanocomposites prepared using isotactic homo PP. As
nanocomposite (mg) (g) wt %
shown in Figure 1b, the clay with organic modification of 25−
NC−iH1−TA 160 4 4.0 30 wt % octadecylamine has lower d001 spacing as compared to
NC−iH2−TA 320 4 8.0 clay having organic modification, 25−30 wt % methyl
NC−aH1−TA 160 4 4.0 dihydroxyethyl hydrogenated tallow ammonium. Further,
NC−aH2−TA 320 4 8.0 nanocomposites prepared with OA as the organic modification
NC−iC1−TA 160 4 4.0 in nanoclay have higher d001 values as compared to the
NC−iC2−TA 320 4 8.0 corresponding nanocomposites prepared with TA as the
NC−iH1−OA 160 4 4.0 organic modification in nanoclay. The microstructure of clay
NC−iH2−OA 320 4 8.0 can be preliminarily determined in accordance with the position
NC−aH1−OA 160 4 4.0 and intensity of characteristic diffraction peak of clay.The
NC−aH2−OA 320 4 8.0 interlayer spacing is calculated by bragg’s law d001 = nλ/(2 sin
NC−iC1−OA 160 4 4.0 θ). Where, n is an integer, λ is wavelength of the incident wave
NC−iC2−OA 320 4 8.0 (1.5404 Å), d001 is the spacing between the planes in the atomic
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Figure 1. XRD pattern of PP−clay nanocomposites prepared from different organic modifications and clay loadings: (a) with isotactic homo PP, (b)
interlayer spacing of clay in nanocomposites, (c) with atactic homo PP, and (d) with ethylene propylene copolymer.

Figure 2. Crystallization and melting behavior of PP−clay nanocomposites prepared from two different organic modifications and clay loadings: (a
and c) isotactic homo PP and (b and d) ethylene propylene copolymer.

lattice, and θ is the angle between the incident ray and the
scattering planes. Further, as shown in Figure 1a, when
prepared with isotactic homo PP, an intercalating type of
composite is obtained. Nanoclay modified with OA has better
10559
ability to intercalate as compared to nanoclay modified with TA
at 4 and 8 wt % clay loading. Figure 1c shows the intercalation
behavior of atactic PP with the type of clay at both 4 and 8 wt
% loadings. In atactic PP also, nanoclay modified with OA has
dx.doi.org/10.1021/ie3007616 | Ind. Eng. Chem. Res. 2012, 51, 10557−10564
Industrial & Engineering Chemistry Research Article

better ability to intercalate. The intercalation behavior of

nanoclay with polymer can be correlated with the chain length
of organic compound used for the modification of clay. The
higher chain length in the case of TA may be causing hindrance
to a polymer chain for intercalation. Nanocomposite prepared
with ethylene−propylene copolymer (Figure 1d) also gives
better intercalation with nanoclay with OA as the organic
modification.
As shown in Figure 1b, ethylene−propylene copolymer has
the highest ability to penetrate between the clay layers. The
spacing (d001) between clay layers in NC−iC1−OA (4.4 nm)
and NC−iC1−TA (4.0 nm) is higher than NC−iH1−OA (4.2
nm) and NC−iH1−TA (3.7 nm), respectively. Nanocompo-
sites prepared with atactic PP have the lowest ability to
penetrate due to their lower bond strength of polymer chain.
With an increase in clay loading from 4 to 8 wt %, the
intercalation ability of the polymer decreases as the amount of
clay available per unit volume is higher. At 4 wt % clay loading
in NC−iC1−OA, the d001 spacing is 4.4 nm, which is decreased
to 3.7 nm in NC−iC2−OA with 8 wt % clay loading. A similar
trend can be seen in Figure 1b for all nanocomposites.
Differential scanning calorimetry (DSC) measurements of
isotactic homo PP, ethylene−propylene copolymer, and
nanocomposites with 4 and 8 wt % clay loading are carried
out to determine the effect of nanoclay on properties such as
heat retardency, crystallization behavior, nucleation effect, etc.
Figure 2a and b shows the crystallization behavior of the virgin
polymer as well as nanocomposites. The crystallization
temperature of virgin isotactic homo PP (V-iH) is 108.4 °C,
which increases to 110.1 °C in NC−iH1−OA and 110.9 °C in
NC−iH1−TA. Further, increasing the amount of nanoclay
loading leads to increasing the crystallization temperature. At 8
wt % clay loading, the crystallization temperature is 111.8 °C
for NC−iH2−OA and NC−iH2−TA. These results are in good Figure 3. TGA curves of PP−clay nanocomposites with nanoclay
agreement with the literature which describes an increase in having two different organic modifications and clay loadings and (A)
crystallization temperature with the addition of nanoclay.19,23 isotactic homo PP, (B) ethylene−propylene copolymer, and (C)
As shown in Figure 2b, nanocomposites prepared with ethylene atactic homo PP.
propylene copolymer also shows similar trends, where
crystallization temperature increases with increase in nanoclay Palza et al.26 have studied PP−spherical silica nanocomposites
loading. Figure 2c and d show the melting behavior of the for improvements in thermal behavior. TGA and DTG
virgin polymer as well as nanocomposites. The heat barrier techniques are extensively used to analyze the nanocomposite.
property is clearly reflected as the peak shift toward higher The peak degradation temperature is found to increase up to 70
temperature with increase in the loading of nanoclay. The type °C, which indicates the thermal stability in the nanocomposite.
of organic modification in nanoclay seems to play a very small The effect of the organic compound present in the clay is
role, as the peak temperature in NC−iH1−TA and NC−iH1− negligible on the initial degradation temperature for NC−iH1−
OA is the same (164.1 °C). A similar trend is observed in TA and NC−iH1−OA which start degrading at the same
nanocomposites prepared with ethylene−propylene copolymer. temperature (459 °C). While NC−iC1−TA and NC−iC1−OA
Degradation of Nanocomposites. Thermogravimetric start degrading at 405 °C, NC−iH2−OA and NC−iH2−TA
analysis (TGA) has been used extensively to throw light on the start at 479 °C. Also, NC−iC2−TA and NC−iC2−OA start at
precise mode of thermal decomposition.24,25 TGA analysis is 424 °C. Leszezynska et al.,27,28 in their review of polymer−
used to measure change in polymer weight as it is heated in montmorillonite (MMT), described factors and mechanisms of
presence/absence of oxygen at a predefined rate of heating. It thermal stability improvement. The “labyrinth” effect limits
can also be used as a kinetic approach to predict polymer oxygen diffusion in the polymer from the outside and also
lifetime under specific test conditions, i.e. the time period restrains the gases evolved in the polymer bulk during
during which the polymer retains its physical properties. Figure degradation. In another effect, MMT catalyzes the degradation
3 shows decomposition curves obtained at heating rate of 20 process leading to a decrease in thermal stability. Few
°C for virgin resin as well as nanocomposites. Nanocomposites hypotheses are proposed for the catalytic effect of MMT in
prepared with isotactic homo PP and ethylene propylene the degradation such as decomposition of organic modifier
copolymer show higher initial degradation temperature as leading to generation of acidic sites in the polymer bulk,
compared to their virgin counterpart. Further, the initial adsorption of water in polyamides, polyesters leading to
degradation temperature increases from 459 to 479 °C with hydrolysis, etc. Nanocomposites prepared with atactic PP do
increases in clay loading from 4 to 8 wt % in isotactic homo PP not show much variation in initial degradation temperature.
and from 405 to 424 °C in ethylene−propylene copolymer. The degradation of virgin resin (V-aH) as well as nano-
10560 dx.doi.org/10.1021/ie3007616 | Ind. Eng. Chem. Res. 2012, 51, 10557−10564
Industrial & Engineering Chemistry Research
composites starts between 360 and 365 °C. This is because in
atactic PP, interchain bonding is much weaker, which is further
affected by the addition of nanoclay. The increase in initial
degradation temperature of nanocomposites indicates that the
life cycle is enhanced to a certain extent with the introduction
of nanoclay, but the degradation process also becomes faster in
nanocomposites as compared to virgin resin. Figure 4 shows
Figure 4. DTG curves of PP−clay nanocomposites with nanoclay
having two different organic modifications and clay loadings and (A)
isotactic homo PP, (B) ethylene−propylene copolymer, and (C)
atactic homo PP.
the differential thermogravimetric curves, where the peak rate
of degradation is calculated in virgin resin and its nano-
composites. The nanocomposites with isotactic homo PP with
4 wt % clay loading has peak rate of degradation at 49 and 56
wt %/min for TA and OA types of clay, respectively. The virgin
resin of isotactic homo PP has peak rate of degradation at 43 wt
%/min. On increasing the clay loading from 4 to 8 wt %, the
peak rate further increases to 57 and 76 wt %/min for TA and
OA types of clay. It is interesting to note that the peak rate of
degradation increases from 43 wt %/min in virgin resin to 76
wt %/min in nanocomposites with 8 wt % clay loading with a
very narrow margin of temperature range between 490 and 500
10561
Article
°C. Hence, it can be said that the nanoclay imparts a
temperature barrier due to its unique layered structure in the
initial phase of the polymer life cycle, but it acts as a catalyst in
the degradation process which enhances the rate of degradation
of polymer in later stage of its life. The enhanced rate of
degradation can be due to the higher amount of residual
impurity in the polymer matrix or because of acid active centers
generated between clay layers.29 Ethylene−propylene copoly-
mer and its nanocomposites also show similar behavior (Figure
4b), where the peak rate of degradation increases from 44 wt
%/min in virgin resin to 74 wt %/min in OA type clay with 8
wt % loading. Similarly the virgin resin of atactic homo PP
(Figure 4c) shows a peak rate of degradation at 38 wt %/min,
which increases to 43 and 40 wt %/min in TA and OA types of
clay, respectively, with 4 wt % clay loading. On further
increasing the clay loading to 8 wt %, the peak rate of
degradation increases to 47 and 63 wt %/min for TA and OA
types of clay, respectively.
The kinetic parameters of degradation such as activation
energy (E), order of decomposition (n), frequency factor
(ln(Z)) are determined through the Friedman technique.30
⎛ dα ⎞ E
ln⎜ ⎟ = ln(Z) + n ln(1 − α) −
⎝ dt ⎠ RT (1)
Where, α is the conversion at time t. R is the gas constant
(8.314 J·mol−1·K−1) and T is the absolute temperature (K).
The plot of ln(dα/dt) vs 1/T is linear with the slope E/(R).
From the slope of the linear plot of ln(1 − α) vs 1/T, E/(nR) is
obtained, which is used to calculate n. Figure 5 shows the plot
of ln(dα/dt) vs 1/T. The plot of isotactic homo PP and its
nanocomposites (Figure 5a) shows a straight line with slope
ranging from 780 to 787 for different nanocomposites.
Activation energy (E) remains almost constant with clay
loading in the polymer matrix (Table 2), as the clay loading in
the polymer matrix increases. The activation energy for virgin
isotactic homo PP is 94 J/mol, which is similar to 94.5 and 94.3
J/mol in TA and OA types of clay, respectively, with 4 wt %
loading. As the clay loading is further increased to 8 wt %, the
value of E is marginally increased to 95.2 and 95.1 J/mol in TA
and OA types of clay, respectively. A similar trend is observed
in nanocomposites with ethylene propylene copolymer (Figure
5b). The virgin resin shows an activation energy of 87.3 J/mol,
which is equivalent to 88.7 and 88.3 J/mol in TA and OA types
of clay, respectively, with 4 wt % clay loadings and 89.5 and
89.2 J/mol when clay loading is increased to 8 wt % in TA and
OA types of clay, respectively. Nanocomposites with atactic PP
show altogether different behavior. Due to weak bonding
strength in the polymer matrix, the weight loss starts at a much
lower temperature ∼300 °C; hence, the DTG plot is also
bimodal (Figure 4b) and the plot of ln(dα/dt) vs 1/T is
parabolic (Figure 5c) instead of a straight line. Further values of
n and ln(Z) are also tabulated in Table 2. The values of n range
from 0.52 to 0.76 in nanocomposites prepared from isotactic
homo PP, while it ranges from 0.48 to 0.75 in nanocomposites
prepared from ethylene−propylene copolymer. With an
increase in clay loading from virgin resin to 4 wt % and further
to 8 wt %, the n values also increase, which indicates an
enhanced order of degradation. Frequency factor ln(Z) is
calculated for each temperature as per eq 1. The average values
are presented in Table 2.
The life cycle of virgin PP and nanocomposites is calculated
using Toop’s equation.31
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Industrial & Engineering Chemistry Research Article

Figure 5. Plot of ln(dα/dt) vs 1/T for the virgin resin and

nanocomposites (A) isotactic homo PP, (B) ethylene−propylene Figure 6. Lifetime of PP−clay nanocomposites: (A) isotactic homo
copolymer, and (C) atactic homo PP. PP, (B) ethylene− propylene copolymer, and (C) atactic homo PP.
Table 2. E, n, and ln(Z) Values Calculated from Friedman
Equation
sample E n ln(Z) composites, with a varied amount of clay loading. Virgin
V-iH 94.0 0.52 9.4 polymer of isotactic homo PP (Figure 6a) shows a lifetime of
NC−iH1−TA 94.5 0.62 10.7 4.7 × 107 min at 260 °C, which decreases to 1.0 × 105 min as
NC−iH1−OA 94.3 0.65 10.5 the temperature increases to 450 °C. On incorporation of 4 wt
NC−iH2−TA 95.2 0.77 11.5 % nanoclay, the lifetime increases to 4.9 × 108 and 4.2 × 108
NC−iH2−OA 95.1 0.76 11.6 min for TA and OA types of clay, respectively, at 260 °C. As
V-iC 87.3 0.48 9.0 the amount of nanoclay incorporation is further increased to 8
NC−iC1−TA 88.7 0.63 9.6 wt %, the lifetime of PP is increased to 9.8 × 1010 and 1.2 ×
NC−iC1−OA 88.3 0.66 9.3 1011 min in TA and OA types of clay, respectively. The increase
NC−iC2−TA 89.5 0.74 10.4 in the lifetime of nanocomposites with an increase in clay
NC−iC2−OA 89.2 0.75 10.1 loading is obvious as the nanoclay imparts better barrier
properties toward environmental conditions. The lifetime of
E ⎡ E ⎤ ethylene−propylene copolymer virgin resin (Figure 6b) is 1.2 ×
ln tf = + ln⎢ P(X f )⎥ 106 min, which increases to 1.0 × 109 min, when clay
RTf ⎣ βR ⎦ (2) incorporation is increased. Figure 6c shows the lifetime of
nanocomposites prepared from atactic homo PP. The atactic
Where, tf is estimated as the time of failure (min), E is PP itself having very much less strength and poor mechanical
activation energy (J/mol), Tf is the failure temperature (K), R is properties does not show significant improvement in lifetime
the gas constant (8.314 J/mol K), P(Xf) is a function whose with incorporation of nanoclay. The virgin atactic PP shows a
values depend on E, and β is heating rate (°C/min). Figure 6 lifetime of 5.6 × 103 min, which is only marginally increased
shows the lifetime of different types of PP and its nano- (8.8 × 103 min) at 8 wt % clay loading.
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Industrial & Engineering Chemistry Research
■
CONCLUSIONS
Three types of PP, namely, atactic homo, isotactic homo, and
ethylene−propylene copolymers are used in the present study.
An aluminosilicate layered type nanoclay with two different
organic modifications (25−30 wt % methyl dihydroxyethyl
hydrogenated tallow ammonium and 25−30 wt % octadecyl-
amine) is used. The virgin polymer and nanocomposites with 4
and 8 wt % clay loading are subjected to stability and
degradation studies. The result indicates that PP−clay nano-
composites bear higher mechanical and barrier properties than
virgin PP. Initiation of degradation is also delayed as revealed in
TGA studies. Furthermore, the lifetime of nanocomposites is
increased with an increasing amount of clay in the polymer
matrix. Further analysis of the weight loss curve through
differential thermogravimetry (DTG) techniques revealed
interesting results. The peak rate of degradation is almost 1.5
times more in nanocomposites with 8 wt % nanoclay
incorporation as compared to its virgin counterpart. This
indicated that as the amount of nanoclay incorporation in the
polymer matrix increased, the rate of degradation also
increased. This can be explained as the degradation in the
polymer starting from the point where the impurity is present
in the matrix. The oxidation/photo-oxidation process in the
polymer matrix starts around the catalyst or any other type of
residual impurity, and slowly, the cracks develop in the matrix,
which leads to disintegration of polymer chains, therefore
degradation. With incorporation of silicate type nanoclay, the
residual impurity in the polymer matrix is increased; hence,
oxidation/photo-oxidation starts from multiple sites leading to
faster degradation of nanocomposites as compared to its virgin
counterpart.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: bag@ched.svnit.ac.in (A.A.M.); akm@ched.svnit.ac.in
(A.K.M.).
Notes
The authors declare no competing financial interest.
■
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