@article{GhobadiHeuchelKratzetal.2012,
  author    = {Ghobadi, Ehsan and Heuchel, Matthias and Kratz, Karl and Lendlein, Andreas},
  title     = {Influence of different heating regimes on the shape-recovery behavior of poly(L-lactide) in simulated thermomechanical tests},
  series = {Journal of applied biomaterials \& functional materials},
  volume    = {10},
  journal   = {Journal of applied biomaterials \& functional materials},
  number    = {3},
  publisher = {Wichtig},
  address   = {Milano},
  issn      = {2280-8000},
  doi       = {10.5301/JABFM.2012.10440},
  pages     = {259 -- 264},
  year      = {2012},
  abstract  = {Aim: Multifunctional polymer-based biomaterials, which combine degradability with a shape-memory capability and in this way enable the design of actively moving implants such as self-anchoring implants or controlled release systems, have been recently introduced. Of particular interest are approved degradable polymers such as poly(L-lactide) (PLLA), which can be easily functionalized with a shape-memory effect. In the case of semicrystalline PLLA, the glass transition can be utilized as shape-memory switching domain. Methods: In this work we applied a fully atomistic molecular dynamics simulation to study the shape-memory behavior of PLLA. A heating-deformation-cooling programming procedure was applied to atomistic PLLA packing models followed by a recovery module under stress-free conditions allowing the shape recovery. The recovery was simulated by heating the samples from T-low = 250 K to T-high = 500 K with different heating rates beta of 125, 40 and 4 K.ns(-1). Results: We could demonstrate that the obtained strain recovery rate (R-r) was strongly influenced by the applied simulation time and heating rate, whereby R-r values in the range from 46\% to 63\% were achieved. On its own the application of a heating rate of 4 K.ns(-1) enabled us to determine a characteristic switching temperature of T-sw = 473 K for the modeled samples. Conclusions: We anticipate that the atomistic modeling approach presented should be capable of enabling further study of T-sw with respect to the molecular structure of the investigated SMP and therefore could be applied in the context of design and development of new shape-memory (bio) materials.},
  language  = {en}
}
@article{GhobadiHeuchelKratzetal.2012,
  author    = {Ghobadi, Ehsan and Heuchel, Matthias and Kratz, Karl and Lendlein, Andreas},
  title     = {Simulation of volumetric swelling of degradable poly[(rac-lactide)-co-glycolide] based polyesterurethanes containing different urethane-linkers},
  series = {Journal of applied biomaterials \& functional materials},
  volume    = {10},
  journal   = {Journal of applied biomaterials \& functional materials},
  number    = {3},
  publisher = {Wichtig},
  address   = {Milano},
  issn      = {2280-8000},
  doi       = {10.5301/JABFM.2012.10432},
  pages     = {293 -- 301},
  year      = {2012},
  abstract  = {Aim: The hydrolytic degradation behavior of degradable aliphatic polyester-based polymers is strongly influenced by the uptake or transport of water into the polymer matrix and also the hydrolysis rate of ester bonds. Methods: We examined the volumetric swelling behavior of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based polyurethanes (PLGA-PU) with water contents of 0 wt\%, 2 wt\% and 7 wt\% water at 310 K using a molecular modeling approach. Polymer systems with a number average molecular weight of M-n = 10,126 g.mol(-1) were constructed from PLGA with a lactide content of 67 mol\%, whereby PLGA-PU systems were composed of five PLGA segments with M-n = 2052 g.mol(-1), which were connected via urethane linkers originated from 2,2,4-trimethyl hexamethylene-1,6-diisocyanate (TMDI), hexamethyl-1,6-diisocyanate (HDI), or L-lysine-1,6-diisocyanate (LDI). Results: The calculated densities of the dry PLGA-PU systems were found to be lower than for pure PLGA. The obtained volumetric swelling of the PLGA-PU was depending on the type of urethane linker, whereby all swollen PLGA-PUs contained larger free volume distribution compared to pure PLGA. The mean square displacement curves for dry PLGA and PLGA-PUs showed that urethane linker units reduce the mobility of the polymer chains, while an increase in backbone atoms mobility was found, when water was added to these systems. Consequently, an increased water uptake of PLGA-PU matrices combined with a higher mobility of the chain segments should result in an accelerated hydrolytic chain scission rate in comparison to PLGA. Conclusions: It can be anticipated that the incorporation of urethane linkers might be a helpful tool to adjust the degradation behavior of polyesters.},
  language  = {en}
}