10.1002/spepro.

003571

The creep behavior of linear low-density polyethylene

Yakov Unigovski, Arthur Bobovitch, Emmanuel Gutman, and Dmytry Mogilansky Research reveals that the creep strain of lms is higher at lower densities, specically between 0.902 to 0.930g/cm3 . The creep behavior of high-density polyethylenewith a density of 0.940.96g/cm3 has been studied extensively,13 while Crissman investigated in detail the long-term creep behavior of linear low-density polyethylene (LLDPE)with a density of 0.933g/cm3 at room temperature, as a function of stress and processing parameters.4, 5 Nevertheless, the effects of variable density, applied stress, morphology, and processing parameters on the creep behavior of LLDPE lms characterized by a broad range of densities have not yet been studied in depth. Therefore, we investigated these processes for 40 and 80 m-thick LLDPE lms with densities of 0.902, 0.912, 0.920, and 0.930g/cm3 (produced by blowing and casting processes) at both room temperature and 70C. We chose strain-to-failure parameterization as a criterion for ductile-creep failure. This parameter is dened as the maximum elongation characterized by necking of the entire sample. At room temperature under a stress of 8MPa, strain to failure increases by one order of magnitude (from 0.08 to 0.80% elongation) for a density decrease from 0.930 to 0.902g/cm3 . We found that the most signicant decrease in total strain and creep compliance occurred with a density increase to more than 0.912g/cm3 , at both room temperature and 70C (see Figure 1). Processing affects creep deformation much less signicantly than density variations. The crystalline structure of cast lms is much more deformed than that of their blown counterparts because of a higher cooling rate in the casting process and a higher orientation in cast lm. This is conrmed by a much broader peak of orthorhombic reection (110) of cast compared to blown lms. Our work suggested that under loading at room temperature, a fraction of the orthorhombic phase in lms with densities of 0.902 and 0.912g/cm3 transforms into the monocline phase. For the latter lm, short-term (0.3h) loading leads to the appearance of a sizeable reection (010) of the monocline phase near an angular orientation of 2 D 19:5 (see Figure 2). For longer test durations, the intensity of the (010) peak decreases slightly and remains unchanged until 165h

Figure 1. (a) Total strain and (b) creep compliance for 10s, J(10), depending on lm density and temperature. RT: Room temperature.

(see Figure 2). Two other monoclinic-phase reections signicantly overlap with the second orthorhombic reection. (Monoclinic reection does not appear at 70C because of the phase instability at elevated temperatures.610 ) However, for the highest-density lm (0.930g/cm3 ), creep load and test temperature do not affect the morphology of the orthorhombic phase. Calorimetric spectra of polyethylene show that the crystallinity percentage and melting-peak temperature of blown lms increase from 29.7 to 39.7% and from 87.0 to 122C, respectively, for a density

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References 1. L. E. Nielsen, The stress dependence of creep of polyethylenes, J. Appl. Polym. Sci. 13, pp. 18001801, 1969. doi:10.1002/app.1969.070130820 2. P. G. Klein, D. W. Woods, and I. M. Ward, The effect of electron irradiation on the structure and mechanical properties of highly drawn polyethylene bers, J. Polym. Sci. B: Polym. Phys. 25 (7), pp. 13591379, 1987. doi:10.1002/polb.1987.090250701 3. J. Rasburn, P. G. Klein, and I. M. Ward, The inuence of short-chain branching on the creep behavior of oriented polyethylene, and its effect on the efciency of crosslinking by electron irradiation, J. Polym. Sci. B: Polym. Phys. 32 (8), pp. 13291338, 1994. doi:10.1002/polb.1994.090320804 4. J. M. Crissman, Effect of processing on uniaxial creep behavior and environmental stress-crack resistance of a linear low-density polyethylene, Polym. Eng. Sci. 29, pp. 15981603, 1989. doi:10.1002/pen.760292209 5. J. M. Crissman, On the long time creep and lifetime behavior in uniaxial extension of a linear low density polyethylene, Polym. Eng. Sci. 31, pp. 541547, 1991. doi:10.1002/pen.760310802 6. E. R. Walter and F. P. Reding, The appearance of a new crystalline phase in stretched, linear polyethylene, J. Polym. Sci. 21, pp. 557559, 1956. doi:10.1002/pol.1956.120219923 7. T. Seto, T. Hara, and K. Tanaka, Phase transformation and deformation processes in oriented polyethylene, Jpn J. Appl. Phys. 7, pp. 3142, 1968. doi:10.1143/JJAP.7.31 8. K. E. Russell, B. K. Hunter, and R. D. Heyding, Monoclinic polyethylene revisited, Polymer 38 (6), pp. 14091414, 1997. doi:10.1016/S0032-3861(96)00643-X 9. J. M. Lagaron, N. M. Dixon, W. Reed, J. M. Pastor, and B. J. Kip, Morphological characterisation of the crystalline structure of cold-drawn HDPE used as a model material for the environmental stress cracking (ESC) phenomenon, Polymer 40, pp. 25692586, 1999. doi:10.1016/S0032-3861(98)00500-X 10. A. L. Bobovitch, A. Sagron, Ya. Unigovski, A. Jarashneli, and E. M. Gutman, Stress relaxation in low-shrink-force polyolen lms, Polym. Eng. Sci. 44, pp. 17161720, 2004. doi:10.1002/pen.20172

Figure 2. X-ray patterns for blown lm with a density of 0.912g/cm3 before (reference) and after creep tests with durations of 0.3 and 165h.

increase from 0.902 to 0.930g/cm3 . The crystallinity of blown lms was slightly higher than that of cast lms of the same density. This can be attributed to a lower cooling rate during the production of blown lms in comparison with cast-lm processing. In summary, the creep strain of lms is higher at lower densities, specically between 0.902 and 0.930g/cm3 . Secondary crystallization of the monoclinic phase (strain-induced crystallization) was found in lms with densities below 0.920g/cm3 under applied stress at room temperature. Cast lms have a less perfect crystalline structure than blown lms. However, processing affects creep much less signicantly than density variations. We continue our characterization of densitydependent creep parameters.

Author Information Yakov Unigovski, Emmanuel Gutman, and Dmytry Mogilansky Ben-Gurion University of the Negev Beer-Sheva, Israel Yakov Unigovski obtained his MSc (1972) and PhD degrees (1978) from Ural State Technical University (Russia). He was appointed a research associate professor (senior scientist) at the Ukrainian National Academy of Sciences in 1993, followed by his current appointment as senior scientist in 1996. Arthur Bobovitch Syfan Saad (99) Ltd. Beer-Sheva, Israel

c 2011 Society of Plastics Engineers (SPE)