@article{DasNoackSchlaadetal.2020,
  author    = {Das, Abhijna and Noack, Sebastian and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Exploring pathways to equilibrate Langmuir polymer films},
  series = {Langmuir},
  volume    = {36},
  journal   = {Langmuir},
  number    = {28},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.0c01268},
  pages     = {8184 -- 8192},
  year      = {2020},
  abstract  = {Focusing on the phase-coexistence region in Langmuir films of poly(L-lactide), we investigated changes in nonequilibrated morphologies and the corresponding features of the isotherms induced by different experimental pathways of lateral compression and expansion. In this coexistence region, the surface pressure II was larger than the expected equilibrium value and was found to increase upon compression, i.e., exhibited a nonhorizontal plateau. As shown earlier by using microscopic techniques [Langmuir 2019, 35, 6129-6136], in this plateau region, well-ordered mesoscopic clusters coexisted with a surrounding matrix phase. We succeeded in reducing Pi either by slowing down the rate of compression or through increasing the waiting time after stopping the movement of the barriers, which allowed for relaxations in the coexistence region. Intriguingly, the most significant pressure reduction was observed when recompressing a film that had already been compressed and expanded, if the recompression was started from an area value smaller than the one anticipated for the onset of the coexistence region. This observation suggests a "self-seeding" behavior, i.e., pre-existing nuclei allowed to circumvent the nucleation step. The decrease in Pi was accompanied by a transformation of the initially formed metastable mesoscopic clusters into a thermodynamically favored filamentary morphology. Our results demonstrate that it is practically impossible to obtain fully equilibrated coexisting phases in a Langmuir polymer film, neither under conditions of extremely slow continuous compression nor for long waiting times at a constant area in the coexistence region which allow for reorganization.},
  language  = {en}
}
@article{DasElTawargyKhechineetal.2019,
  author    = {Das, Abhijna and El-Tawargy, Ahmed S. and Khechine, Emna and Noack, Sebastian and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Controlling Nucleation in Quasi-Two-Dimensional Langmuir Poly(L-lactide) Films through Variation of the Rate of Compression},
  series = {Langmuir},
  volume    = {35},
  journal   = {Langmuir},
  number    = {18},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.9b00619},
  pages     = {6129 -- 6136},
  year      = {2019},
  abstract  = {We studied morphological changes in a quasi-two-dimensional Langmuir film of low molar mass poly(L-lactide) upon increasing the surface density, starting from randomly distributed molecules to a homogeneous monolayer of closely packed molecules, followed by nucleation and growth of mesoscopic, three-dimensional clusters from an overcompressed monolayer. The corresponding nucleation density of mesoscopic clusters within the monolayer can be tailored through variation of the rate of compression. For a given surface density and temperature, the nucleation probability was found to increase linearly with the rate of compression, allowing to adjust the density of mesoscopic clusters over nearly 2 orders magnitude.},
  language  = {en}
}
@article{ChandranDoldBuvignieretal.2015,
  author    = {Chandran, Sivasurender and Dold, Stefanie and Buvignier, Amaury and Krannig, Kai-Steffen and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States},
  series = {Langmuir},
  volume    = {31},
  journal   = {Langmuir},
  number    = {23},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.5b01212},
  pages     = {6426 -- 6435},
  year      = {2015},
  abstract  = {Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films.},
  language  = {en}
}