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 2nd International Symposium on Frontier of Applied Physics (ISFAP 2016) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 817 (2017) 012020 doi:10.1088/1742-6596/817/1/012020

International Conference on Recent Trends in Physics 2016 (ICRTP2016) IOP Publishing

Journal of Physics: Conference Series 755 (2016) 011001 doi:10.1088/1742-6596/755/1/011001

Activation energy determination in multi-frequency dynamic

molecular interaction analysis of PEG 4000-Cristobalite
composites using DMA

N A Fauziyah, T A Fadly, A Rosyidi, Mashuri and S Pratapa

Departement of Physics, Faculty of Mathematics and Sciences, Institute of
Technology Sepuluh Nopember, Surabaya 60111 Indonesia

E-mail: [email protected]

Abstract. Degradation activation energy of PEG-Cristobalite composites was investigated

using Dynamic Mechanical Analysis (DMA) instrument at multi-frequency shear mode. The
applied frequencies were 1, 10, 100, and 200 Hz. The cristobalite of as much as 20% and 40%
by weight was used as the filler of the composites, while PEG 4000 was the matrix. Results
showed that additional of cristobalite improved the storage modulus (G’) of the composites
almost five times of the pure PEG 4000. Moreover, such addition and higher applied frequency
shifted glass transition temperature (Tg) to higher values. Furthermore, the multi-frequency
measurement provided the degradation activation energy of the samples, where the highest
value was reached by the 40% sample, i.e. 571.4 kJ. This result implied that there was a certain
energetic barrier from the filler that the structural units of polymer need to surmount
collectively before its viscous flow occured.

1. Introduction
Research focus in modern polymeric materials includes thermal stability as well as physical and
mechanical properties at high temperature. The thermal stability of polymers is connected not only
with the initial degradation temperature (Tg) [1], but also, with dislocations due to mechanic and
thermal treatment [2]. In particular, the apparent activation energy (Ea) is of great importance aspect of
degradation of such materials [3].
DMA technique is useful in characterizing polymer degradation as a function of frequency,
temperature, time, stress or a combination of these parameters [4-6]. The dynamic mechanical
responses of degradation are usually observed at temperatures near (or, in some cases, above) the
melting point. As a result, the lifetime predictions based on these measurements can be determined.
DMA response also depends on the physical or structural arrangement of phases such as interface,
morphology and the nature of the constituents [4,5]. In particular, the effect of filler, fibre content,
fibre orientation in fibre-reinforced composite materials has been extensively studied [7,8].
Cristobalite is a metastable silica polymorph. It exists at room temperature but easily transformed
into quartz at high temperature. There is no study on the utilization of cristobalite as a filler in a
composite system. This phase is very unique since it exhibits a negative Poisson’s ratio [9-12].
Materials with a negative Poisson’s ratio (called auxetic material) have a counterintuitive behaviour of
becoming wider when stretched and thinner when compressed [12]. This behaviour has many
beneficial effects on the materials’ macroscopic properties (e.g., increased indentation resistance, a

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 2nd International Symposium on Frontier of Applied Physics (ISFAP 2016) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 817 (2017) 012020 doi:10.1088/1742-6596/817/1/012020

natural ability to form “dome-shaped” surfaces) that make them superior in many practical
applications [10-11].
Research on polyethilene glycol (PEG)-based functional polymer-ceramic composites is relatively
extensive. For example, SiO2–PEG–3-isocyanato-propyltrietoxysilane nanocomposite was prepared as
hydrophilic films [13]. Qian et. al. [14] also reported green shape-stabilized composite phase change
material (PCM) of PEG/SiO2 with enhanced thermal performance based on oil shale ash via
temperature-assisted sol–gel method. They did not, however, determine the crystalline phase of SiO2
in their studies. In our previous work, we reported the effect of quartz content on the PEG 4000-quartz
composites using DMA in shear mode [15]. Quartz is a polymorph of silica which is chemically stable
and exhibits positive Poisson’s ratio. The dynamic mechanical responses using multi-frequency DMA
of such composites are reported elsewhere [16]. However, the multi-frequency DMA measurements
for PEG 4000-cristobalite composites have not been investigated yet.
In this report, we describe thermal degradation experiments of PEG 4000-cristobalite composites.
The low melting point PEG 4000, i.e. Tm= 60-63 ºC [15], [17] was used as the matrix, while
cristobalite which was processed from natural silica sand was the filler. The activation energy
determination was investigated through DMA measurements in shear mode at various frequency.

2. Experimental

2.1. Sample preparation

Cristobalite powder was prepared by purifying silica sand from Tanah Laut, Pelaihari, South
Kalimantan. Polyethylene Glycol 4000 (Merck Schuchardt OHG 85662 Hohenbrunn, Germany) was
used as matrix in this composite. Magnetic separation and immersion with HCl 2M was done to purify
silica sand and get SiO2 quartz powder. Next step, precursor quartz powder was copresipited by using
NaOH. In order to get SiO2 crystobalite (SC), copresipited powder was calcined at 950ºC under the air
for 8 hours. All of those phases were identified by using X-Ray Diffractometer (XRD). The composite
samples were prepared by mixing SC powder (as much as 20% and 40% by weight) as the filler in
PEG 4000 and then followed by casting in pellet forms. A pure PEG 4000 sample was also prepared
for comparison.

2.2. DMA measurement

Composite samples were casted in small-dimension, 1 mm thickness and (5 mm  5 mm) square
which were compatible with the geometry and dimensions for DMA testing in shear mode. The
experiment has been described elsewhere [15]. For each composite sample was heated at 50ºC to
increase samples necking after considering the theoretical melting point of PEG 4000. The mechanical
properties of composite samples were measured using DMA Mettler Toledo instrument. From our
initial experiments, the range temperature was about 25ºC until 80ºC with multi-frequency as
oscillation responses (1, 10, 100, and 200 Hz). This range required to investigated dynamic responses
from composites.

3. Results and discussion

Figures 1, 2, and 3 show comparative storage moduli (G’) of the composite samples at various
frequencies as a function of temperature, as well as those for pure PEG samples. In general, G’ drops
as temperature increases. The decline is very sharp around 50-65ºC for all samples. A decline in G’ is
often associated with a reduction in viscosity and resistance of the materials toward deformation. In
glassy region (see figure 1) is often related to the toughness with high viscosity. As incresing
temperature continues increasing free motion of polymer chain. As heating continues, it will reach Tg
(glass transition). In this region, Tg presents a major transition for drastically from glassy region to
rubbery state. For thermoplastic, degradation continues after Tg because of light cross-links in polymer
chain (it can be seen in rubbery plateau from figure 1) [18].

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 2nd International Symposium on Frontier of Applied Physics (ISFAP 2016) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 817 (2017) 012020 doi:10.1088/1742-6596/817/1/012020

Figure 1. Storage modulus of pure PEG 4000 in multi-frequency (1, 10, 100, 200 Hz)

Figure 2. Storage modulus of composite Figure 3. Storage modulus of composite

20wt% cristobalite in multi-frequency (1, 10, 40wt% cristobalite in multi-frequency (1, 10,
100, 200 Hz) 100, 200 Hz)

As can be compared from figures 1, 2, and 3, the highest G’ is achieved by 40 wt% cristobalite. Its
G’ value is five times of that of pure PEG. This phenomenon can be attributed to crosslinking between
PEG and cristobalite. The effects of crosslinking on the various regions of the DMA curve are visible
in the rubbery and glass transition regions. However, the effect is not visible in the glassy region.
Thus, highly cross-linked thermoplastic polymer has much larger storage modulus indicating the
tighter network structure and higher stiffness while that with light cross-links shows a considerably
smaller storage modulus [7,19].
When various frequencies are applied, G’ drop shifts to higher temperature for all samples – as
shown by solid arrows in figures 1-3. The shift therefore indicates changes in Tg. The higher the
frequency the higher Tg. Tg values for all samples are presented in table 1. The shift to higher
temperature is a direct consequence of polymer to achieve (rubbery) equilibrium state. The polymer
chain motions are constrained at high frequency but become more liberated at low frequency [18,20].
Consequently, higher Tg is required for a sample to achieve a mechanical equilibrium state at high
frequency load.

3
 2nd International Symposium on Frontier of Applied Physics (ISFAP 2016) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 817 (2017) 012020 doi:10.1088/1742-6596/817/1/012020

Table 1. Tg value of PEG 4000-cristobalite in multi-frequency

1Hz 10 Hz 100 Hz 200 Hz

PEG 4000 43.00 45.50 47.70 54.98

SC 20 47.00 49.34 53.75 57.56
SC 40 48.00 51.87 53.95 56.60

The resulting set of experimental Tg data (table 1) was used to determine the apparent activation
energy (Ea) of material degradation. Using Arrhenius equation [21].
𝐸𝑎
ln 𝑓 = 𝑅𝑇 (1)
where f = applied frequency, R = general gas constant, and T = degradation temperature (here we used
Tg), plots between ln(f) and 1000/T for all samples are presented in figure 4. Ea can be obtained from
the slope of the plots. The Ea value for each sample is shown in figure 4, where in general increases
with cristobalite content. Higher Ea value implies higher energy to initiate degradation [20]. The
presence of cristobalite crystals inhibits the degradation in the composite. In particular, cristobalite
prevents the free motions of the PEG polymer chains.

Figure 4. Ea value of composites 20 and 40 wt% cristobalite.

4. Conclusion
Since this study we can investigate dynamic mechanical behaviour by using multi-frequency DMA.
Minimum degradation material energy (Ea) can be obtained by using arrhenius equation. The highest
Ea value was reached by 40 wt% cristobalite. Adding cristoballite as filler is highly effective to
increase degradation themperatur of composites.

Acknowledgements
The author acknowledges to Ministry of Research Technology and High Education of the Republic of
Indonesia and LPPM ITS to support finance through program PUPT-2016 No.
01751/IT2.11/PN.08/2016. Also a great thanks to Departement of Physics, Institute of Technology
Sepuluh Nopember (ITS) to support this work.

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 2nd International Symposium on Frontier of Applied Physics (ISFAP 2016) IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 817 (2017) 012020 doi:10.1088/1742-6596/817/1/012020

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