High-density polyethylene/fullerene (HDPE/C60) nanocomposites with the C60 loading that varied from 0.5 to 5.0% by weight were prepared via melt compounding. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) results showed that the presence of C60 could remarkably enhance the thermal properties of HDPE. A very low C60 loading (0.5 wt%) increased the onset degradation temperature from 3 8 9 C to 4 5 9 C and decreased the heat release from 3176 J/g to 1490 J/g. The larger the loading level of C60, the better the thermal stability of HDPE/C60 nanocomposites. Rheological investigation results showed that the free radical trapping effect of C60 was responsible for the improved thermal stability of HDPE.

1. Introduction

Soon after the discovery of buckminsterfullerene, C60, it was able to be produced in bulk quantities, which inspired scientists worldwide to explore its fascinating chemistry, and it has now become the most intensely researched single molecule in modern science [13]. A significant aspect of the C60 chemistry is its high reactivity towards free radicals, and C60 has 30 carbon-carbon double bonds which can trap more than 34 free radicals; thus it is known as a radical sponge [4]. The free radical reaction of C60 with various compounds has been extensively studied [47].

Since the thermal degradation of polymers is a free radical chain reaction, the presence of C60 in polymer may trap the free radicals produced during the degradation process. These suggest the possible use of fullerene as an effective radical scavenger in chain reactions during thermal degradation. It has been reported that 2 wt% fullerene (C60) could increase the onset degradation temperature ( 𝑇 o n s e t ) and the maximum degradation temperature ( 𝑇 m a x ) of PP by 20 and 62°C, respectively [8, 9]. The presence of C60 could delay the thermal oxidation and improve the thermal stability of PP, which could be attributed to the high reactivity of C60 towards free radicals.

The present paper mainly focused on studying the influence of C60 on the thermal degradation behavior and rheological properties of high-density polyethylene. Concerning that the thermal degradation of polyethylene is done also via a free radical chain scission process as PP, C60 is expected to have positive effect on improving the thermal stability of PE.

2. Materials and Methods

2.1. Materials

High-density Polyethylene (HDPE, 5000 S, MFR = 0.9 g/10 min) was purchased from Yangzi Petrochemical Co., Ltd, and C60 (purity: >99%) was bought from Henan Puyang Co., Ltd.

2.2. Preparation of HDPE/C60 Nanocomposites

HDPE/C60 nanocomposites were prepared via melt compounding at 180°C in a ThermoHaake rheomixer with a rotor speed of 60 rpm for 8 min. Nanocomposites containing 0.5 wt%, 1.0 wt%, 2.5 wt%, and 5.0 wt% C60 were designated as C60-0.5%, C60-1.0%, C60-2.5%, and C60-5.0%.

2.3. Measurements and Characterization

Thermogravimetric analysis (TGA) was performed on a STA 409 PC thermal analyzer at a heating rate of 20°C/min in air atmosphere and N2 atmosphere, with a scanning range from 30 to 700°C, and each specimen was examined in triplicate.

The rheological properties of HDPE and its nanocomposites were conducted on a controlled strain rheometer (Haake MARS) in air environment. The samples were pressed at 180°C under 15 MPa to get the disklike specimens with 25 mm in diameter and 1.2 mm in thickness. The isothermal dynamic frequency sweeps were performed under the condition of the frequency range, strain amplitude, and temperature being 100–0.01 rads−1 with the strain of 1% at 180°C and 300°C, respectively. Temperature scanning test was performed in the range from 180 to 300°C with the 1% strain and a fixed frequency at 1 rads−1.

The dispersion of C60 in the HDPE matrix was observed by transmission electron microscopy (TEM, JEM-1200EX).

3. Results and Discussion

3.1. Dispersion of C60 in HDPE Matrix

The diameter of the spherical C60 molecule is 0.71 nm, and its crystal size differs with different methods of fabrication [9]. Figure 1 shows the TEM images for pure C60 and C60-5%. The size of C60 crystals used in this work from Figure 1(a) is from 70 to 200 nm. From Figure 1(c), it is shown that many of C60 crystallites in the HDPE matrix were shaped in ellipsoidal, rodlike. This phenomenon may be caused by the strong shear force during blending. The shear force could destroy the primary stack of C60 crystallites and these crystallites rearrange to different type. In the HDPE matrix, C60 crystallites aggregates and does not disperse well through melt blending, as observed from Figure 1(b). The size of some C60 domains in nanocomposites is about 500 nm or even large.

3.2. Thermal Properties of HDPE/C60 Nanocomposites

The thermal stability of HDPE and HDPE/C60 nanocomposites was tested by TGA, and their TG and DTG curves in nitrogen atmosphere are shown in Figure 2, with detailed data listed in Table 1. At the initial stage of degradation (before 400°C), C60 reacts easily with low-molecular-weight alkyl radicals with formation of remarkable persistent products RnC60    (where 𝑛 = 1 , 2 , 3 ) [10, 11], which caused that the decomposition of HDPE/C60 nanocomposites is slower than pure HDPE. The onset thermal decomposition temperature ( 𝑇 o n s e t ) of HDPE is noticeably increased with the addition of C60. For example, the 𝑇 o n s e t of C60-0.5% is 459°C, about 70°C higher than pure HDPE. With increasing C60 content, the onset temperature of HDPE/C60 nanocomposites changes slightly. From DTG curves, the maximum decomposition temperature ( 𝑇 m a x ) is obtained, with 𝑇 m a x 497°C for C60-0.5%, about 14°C higher than pure HDPE.

Figures 3 and 4 present the TG and DSC curves for HDPE and its composites in air atmosphere, with detailed data given in Table 2. In air atmosphere, the presence of oxygen could enhance the thermal oxidation decomposition of HDPE nanocomposites remarkably. HDPE experiences a rapid thermal oxidation decomposition accompanied by hydrogen abstraction [12]. The ( 𝑇 o n s e t ) of HDPE is about 323°C, and two-step decomposition processes are observed at around 398°C and 456°C (see Table 2). The first step decomposition is the oxidation of HDPE [13]. The second step may be the decomposition of oxidation products formed by the oxidation of HDPE. C60, as the radical sponge, could capture the free radicals produced during the degradation process. Obviously, the presence of C60 delays the oxidation degradation of parent polymer and the first-step 𝑇 m a x disappears, and the 𝑇 o n s e t of the nanocomposites noticeably increase with the increase of C60 content. As for C60-2.5%, its 𝑇 o n s e t is around 431°C, 108°C higher than pure HDPE, which indicates that the presence of C60 slows down the thermal oxidation decomposition of HDPE remarkably. However, when the contents of C60 in the matrix exceed 2.5 wt%, the 𝑇 o n s e t of the nanocomposites decreases with the content of C60. At high loading (as for C60-5.0%), C60 may tend to attract each other, which causes the agglomeration (as shown in Figure 1) instead of trapping the alkyl fragments radicals bringing down the thermal stability of HDPE/C60 nanocomposites.

The difference in thermal behavior between air and nitrogen atmospheres indicates that the presence of oxygen could speed up the thermal oxidation decomposition of HDPE nanocomposites remarkably. The oxygen and alkyl fragment radicals trapped by C60 in nanocomposites during the thermal decomposition are competitive.

DSC measurements could provide the heat enthalpy of thermal degradation during the decomposition process of materials. Figure 4 presents the DSC curves of HDPE/C60 nanocomposites in air atmosphere. In air atmosphere, HDPE/C60 nanocomposites experiences rapid exothermal oxidation decomposition at high temperature. The enthalpy ( Δ H 𝑑 ) is an important parameter since it could quantify the heat evolution produce in the process of oxidation decomposition. The enthalpies of the nanocomposites are greatly reduced from 3176 J/g for HDPE to 1490 J/g for C60-0.5%, indicating that the nanocomposites release much less heat in the process of oxidation dehydrogenization and this phenomenon is favorable to flame retarded polymer materials.

3.3. Mechanism for the Thermal Stability of HDPE/C60 Nanocomposites

In order to clarify the mechanism for C60 improving the thermal stability of HDPE, the rheological measurements were introduced to investigate the viscoelastic behaviors of the nanocomposites. For investigating the viscoelastic behavior of the nanocomposites in the heating process, temperature scanning measurements were performed. Figure 5 presents the curves of temperature dependence of complex viscosity ( 𝜂 ) for HDPE and its nanocomposites. Clearly, with the increase of temperature, the complex viscosity ( 𝜂 ) of nanocomposites decreases, and then increases sharply. The critical temperature is defined as 𝑇 c , at which 𝜂 starts to increase or crosslink reaction occurs. The easier movement of polymer chains during heating, or the occurrence of degradation of polymer can cause the decrease of 𝜂 . The increase of 𝜂 is due to the occurrence of an oxidation crosslink or the oxidation crosslink reaction overwhelming the polymer decomposition. In the case of pure HDPE, it gives a 𝑇 c of 285°C. For HDPE/C60 nanocomposites, their 𝑇 c is about 45°C lower than that of HDPE, implying that another kind of crosslink reaction occurred in the process of heating for HDPE/C60 systems, which speeds up the crosslink reaction whether before or after oxidation crosslinking takes place.

The viscoelastic behaviors of the nanocomposites at 180°C were studied and those of parent polymer, HDPE, were also used as a comparison. Figures 6 and 7 show the storage moduli ( 𝐺 ) and complex viscosity ( 𝜂 ) as a function of frequency ( 𝜔 ) of HDPE and its nanocomposites. Some researchers have found that both 𝐺 and 𝜂 have much larger values than those of parent polymers in the low 𝜔 regime for the nanocomposites containing CNTs [1417] or clay [18, 19], suggesting that the presence of CNTs or clay affects the relaxation and motion of polymer chains due to their spatial geometry. Most authors attribute these viscoelastic behaviors to the formation of CNT or clay networks in the polymer matrix. However, in the high 𝜔 region, the addition of CNTs and clay does not significantly affect the 𝐺 or 𝜂 of polymers. Unlike CNTs and clay, whether in the low 𝜔 region or high 𝜔 region, not much obvious difference in 𝐺 and 𝜂 is observed for the HDPE/C60 nanocomposites with various C60 contents. The oxidation degradation of HDPE does not occur at 180°C (as shown in Figure 3 and Table 2). And not enough free radicals react with C60. Therefore, the incorporation of C60 does not affect the movement and relaxation of polymer chain segments remarkably.

The viscoelastic behaviors of the nanocomposites at 300°C after dynamic temperature scanning measurements were also studied. Figures 8 and 9 show the storage moduli ( 𝐺 ) and complex viscosity ( 𝜂 ) as a function of frequency ( 𝜔 ) of HDPE and its nanocomposites at 300°C. The increase of complex viscosity with C60 content is concomitant with the increase of the storage moduli. The storage moduli for the nanocomposites show a monotonic increase at all frequencies with increasing C60 content. The 𝐺 versus frequency curve for the nanocomposites appears to be approaching a plateau at low frequencies. It has been proposed that this “plateau” effect is derived from interconnected structures of isometric fillers that result in an apparent yield stress which is manifest by a plateau in either 𝐺 or 𝜂 versus frequency plots [20, 21]. Exposed at 300°C for a long time, many alkyl radicals appear, coupled with the interfacial interactions between free radicals and C60. The restraint for the move and relaxation of polymer chains increased 𝐺 and 𝜂 , which is the evidence for the presence of a chemical reaction between the HDPE matrix and C60.

4. Conclusion

The presence of C60 could enhance the thermal stability of HDPE. A very low C60 loading (0.5 wt%) increases the 𝑇 o n s e t from 389°C to 459°C and decreases the heat release from 3176 J/g to 1490 J/g. The free radical trapping effect of C60 is responsible for the improved thermal stability of HDPE. Thus, C60 is expected to be an efficient thermal stabilizer to the polymer materials that degraded with a free radical chain scission process.


This work was financially supported by the National Natural Science Foundation of China (no. 51073140).