Multiple shape-memory behavior and thermal-mechanical properties of peroxide cross-linked blends of linear and short-chain branched polyethylenes

Thermally induced shape-memory effect (SME) in tensile mode was investigated in binary and ternary blends of two ethylene-1-octene copolymers with a degree of branching of 30 and 60 CH3/1000C and/or nearly linear polyethylene cross-linked after melt mixing with 2 wt% of liquid peroxide 2,5-dimethyl-2,5-di-(tert.butylperoxy)-hexane at 190°C. The average cross-link density estimated by means of the Mooney-Rivlin equation on the basis of tensile test data was character- ized between 130 and 170 mol·m-3 depending on the blend composition. Thermal analysis points out multiple crystalliza- tion and melting behavior of blends caused by the existence of several polyethylene crystal populations with different perfection, size and correspondingly different melting temperature of crystallites. That agrees well with the diversity of blends phase morphology characterized by atomic force microscopy. However, triple- and quadruple-SME could be observed only after two- and accordingly three-step programming of binary and tertiary blends, respectively, at suitable temperatures and strains. Compared to performances obtained for the same blend after single-step programming above the maximal melting temperature the significantly poorer characteristics of SME like strain fixity and strain recovery ratio as well as recovery strain rate occurred after multi-step programming.

[1]  Ingo Bellin,et al.  Dual-shape properties of triple-shape polymer networks with crystallizable network segments and grafted side chains , 2007 .

[2]  M. Hoffmann Der Einfluß von Verhakungen auf das Dehnungsverhalten von vernetzten Polymeren , 1972 .

[3]  P. J. Phillips,et al.  Peroxide crosslinking of linear low‐density polyethylenes with homogeneous distribution of short chain branching , 1995 .

[4]  A. Lendlein,et al.  Shape-memory polymers. , 2002, Angewandte Chemie.

[5]  J. Bang,et al.  Melt‐state miscibility of poly(ethylene‐co‐1‐octene) and linear polyethylene , 2008 .

[6]  Feng-kui Li,et al.  Shape memory effect of ethylene–vinyl acetate copolymers , 1999 .

[7]  D. Ratna,et al.  Recent advances in shape memory polymers and composites: a review , 2008 .

[8]  S. Ota Current status of irradiated heat-shrinkable tubing in Japan , 1981 .

[9]  D. J. Montgomery,et al.  The physics of rubber elasticity , 1949 .

[10]  Mao Xu,et al.  Shape memory effect of polyethylene/nylon 6 graft copolymers , 1998 .

[11]  A. Hiltner,et al.  Classification of homogeneous ethylene‐octene copolymers based on comonomer content , 1996 .

[12]  R. Langer,et al.  Polymeric triple-shape materials , 2006, Proceedings of the National Academy of Sciences.

[13]  T. Hjertberg,et al.  Effect of molecular structure and topology on network formation in peroxide crosslinked polyethylene , 2003 .

[14]  R. Langer,et al.  Biodegradable, Elastic Shape-Memory Polymers for Potential Biomedical Applications , 2002, Science.

[15]  B. Wunderlich,et al.  A Study of Annealing of Poly(ethylene-co-octene) by Temperature-Modulated and Standard Differential Scanning Calorimetry , 1999 .

[16]  J. Menczel,et al.  Memory effect of low-density polyethylene crystallized in a stepwise manner , 1976 .

[17]  Marc Behl,et al.  Actively moving polymers. , 2006, Soft matter.