Tuning Chain Relaxation from an Amorphous Biopolymer Film to Crystals by Removing Air/Water Interface Limitations.

A promising route to the synthesis of protein-mimetic materials that are capable of strong mechanics and complex functions is provided by intermolecular ß-sheet stacking. An understanding of the assembly mechanism on ß-sheet stacking at molecular-level and the related influencing factors determine the potential to design polymorphs of such biomaterials towards broad applications. Herein, we quantitatively reveal the air/water interface (AWI) parameters regulating the transformation from crowding amorphous aggregates to ordered phase and show that the polymorph diversity of ß-sheet stacking is regulated by the chain relaxation-crystallization mechanism. An amorphous macroscale amyloid-like nanofilm is formed at the AWI, in which unfolded protein chains are aligned in a short-range manner to form randomly packed ß-sheets. The subsequent biopolymer chain relaxation-crystallization to form nanocrystals is further triggered by removing the limitations of energy and space at the AWI.

Cobalt nanoparticles growth on a block copolymer thin film: a time-resolved GISAXS study.

Cobalt sputter deposition on a nanostructured polystyrene-block-poly(ethylene oxide), P(S-b-EO), template is followed in real time with grazing incidence small-angle X-ray scattering (GISAXS). The polymer template consists of highly oriented parallel crystalline poly(ethylene oxide) (PEO) domains that are sandwiched between two polystyrene (PS) domains. In-situ GISAXS shows that cobalt atoms selectively decorate the PS domains of the microphase-separated polymer film and then aggregate to form surface metal nanopatterns. The polymer template is acting as a directing agent where cobalt metal nanowires are formed. At high metal load, the characteristic selectivity of the template is lost, and a uniform metal layer forms on the polymer surface. During the early stage of cobalt metal deposition, a highly asymmetric nanoparticles agglomeration is dominating structure formation. The cobalt nanoparticles mobility in combination with the high tendency of the nanoparticles to coalescence and to form immobile large-sized particles at the PS domains are discussed as mechanisms of structure formation.

Influence of nanoparticle surface functionalization on the thermal stability of colloidal polystyrene films.

The installation of large scale colloidal nanoparticle thin films is of great interest in sensor technology or data storage. Often, such devices are operated at elevated temperatures. In the present study, we investigate the effect of heat treatment on the structure of colloidal thin films of polystyrene (PS) nanoparticles in situ by using the combination of grazing incidence small-angle X-ray scattering (GISAXS) and optical ellipsometry. In addition, the samples are investigated with optical microscopy, atomic force microscopy (AFM), and field emission scanning electron microscopy (FESEM). To install large scale coatings on silicon wafers, spin-coating of colloidal pure PS nanoparticles and carboxylated PS nanoparticles is used. Our results indicate that thermal annealing in the vicinity of the glass transition temperature T(g) of pure PS leads to a rapid loss in the ordering of the nanoparticles in spin-coated films. For carboxylated particles, this loss of order is shifted to a higher temperature, which can be useful for applications at elevated temperatures. Our model assumes a softening of the boundaries between the individual colloidal spheres, leading to strong changes in the nanostructure morphology. While the nanostructure changes drastically, the macroscopic morphology remains unaffected by annealing near T(g).

Structure and macroscopic tackiness of ultrathin pressure sensitive adhesive films.

Ultrathin layers of the statistical copolymer P(nBA-stat-MA) with a majority of n-butyl acrylate (nBA) and a minority of methyl acrylate (MA) are characterized with respect to the film morphology and the mechanical response in a probe tack test. The probed copolymer can be regarded as a model system of a pressure sensitive adhesive (PSA). The films are prepared by spin-coating which enables an easy thickness control via the polymer concentration of the solution. The film thickness is determined with x-ray reflectivity (XRR) and white light interferometry (WLI). Grazing incidence small angle x-ray scattering (GISAXS) provides detailed and statistically significant information about the film morphology. Two types of lateral structures are identified and no strong correlation of these structures with the PSA film thickness is observed. In contrast, prominent parameters of the probe tack test, such as the stress maximum and the tack energy, exhibit an exponential dependence on the film thickness.