Morphologie und Wachstumskinetik von Crazes in amorphen Polymeren

Zusammenfassung Im vorfibrillaren Stadium besitzt die Crazematerie eine in Verformungsrichtung deformierte Netzwerkstruktur, die sich bei Polystyrol und Styrol-Acrylnitril-Copolymerisat elektronenoptisch an Oberflächenabdrücken sauerstoffionengeätzter Proben nachweisen läßt. Während die durchschnittlichen Globulitverformungen zumeist deutlich unterhalb von 50% liegen, werden partiell Spitzenwerte von bis zu 300% erreicht. Am Beispiel des Polystyrols verdeutlichen quantitative Strukturvergleiche mit warmgerecktem Material, daß die molekulare Beweglichkeit während des Crazewachstums und der Schulter-Hals-Verstreckung derjenigen entspricht, die für thermisch aktiviertes Material oberhalb der Glastemperatur charakteristisch ist.Mit 7 Abbildungen und 2 Tabellen     

Porosity Switching in Polymorphic Porous Organic Cages with Exceptional Chemical Stability

Porous solids that can be switched between different forms with distinct physical properties are appealing candidates for separation, catalysis, and host–guest chemistry. In this regard, porous organic cages (POCs) are of profound interest because of their solution‐state accessibility. However, the application of POCs is limited by poor chemical stability. Synthesis of an exceptionally stable imine‐linked (4+6) porous organic cage ( TpOMe‐CDA ) is reported using 2,4,6‐trimethoxy‐1,3,5‐triformyl benzene (TpOMe) as a precursor aldehyde. Introduction of the ‐OMe functional group to the aldehyde creates significant steric and hydrophobic characteristics in the environment around the imine bonds that protects the cage molecules from hydrolysis in the presence of acids or bases. The electronic effect of the ‐OMe group also plays an important role in enhancing the stability of the reported POCs. As a consequence, TpOMe‐CDA reveals exceptional chemical stability in neutral, acidic and basic conditions, even in 12 m NaOH. Interestingly, TpOMe‐CDA exists in three different porous and non‐porous polymorphic forms (α, β, and γ) with respect to differences in crystallographic packing and the orientation of the flexible methoxy groups. All of the polymorphs retain their crystallinity even after treatment with acids and bases. All the polymorphs of TpOMe‐CDA differ significantly in their properties as well as morphology and could be reversibly switched in the presence of an external stimulus.     

Hydrophobic Poly(tert‐butyl acrylate) Photonic Crystals towards Robust Energy‐Saving Performance

Photonic crystals (PCs) have been widely applied in optical, energy, and biological fields owing to their periodic crystal structure. However, the major challenges are easy cracking and poor structural color, seriously hindering their practical applications. Now, hydrophobic poly(tert‐butyl acrylate) (P(t‐BA)) PCs have been developed with relatively lower glass transition temperature (T_g), large crack‐free area, excellent hydrophobic properties, and brilliant structure color. This method based on hydrophobic groups (tertiary butyl groups) provides a reference for designing new kinds of PCs via the monomers with relatively lower T_g. Moreover, the P(t‐BA) PCs film were applied as the photoluminescence (PL) enhanced film to enhance the PL intensity of CdSe@ZnS QDs by 10‐fold in a liquid‐crystal display (LCD) device. The new‐type hydrophobic force assembled PCs may open an innovative avenue toward new‐generation energy‐saving devices.     

Attrition and particle breakage under monotonic and cyclic loadingAttrition et rupture de particules sous chargements monotones et cycliques

The morphological evolution of gravel grains under monotonic and cyclic loading, typically present in road structures, is presented. Two types of mineralogy are considered: a limestone and a sandstone. Loading in uniaxial strain conditions are applied, with a maximum mean pressure of 5 MPa and a maximum number of cycles of 250?000. Variations in grain size distribution and grain shape, measured with image analysis techniques, are discussed in detail. In the case of uniform grain size distribution, particle breakage does appear for stresses around 500 kPa for the limestone grains and 100 kPa for the sandstone grains. For well-graded materials under low cyclic pressures (<1 MPa), changes in grain size distribution can hardly be detected. To cite this article: F. Mayoraz et al., C. R. Mecanique 334 (2006).     

Evolution of the Ligand Shell Morphology during Ligand Exchange Reactions on Gold Nanoparticles

Ligand exchange reactions are used to achieve nanoparticles coated with a mixture of ligand molecules. Currently, nothing is known on the evolution of the morphology of the ligand shell during the reaction. Here, we use a recently developed method (based on MALDI‐TOF) to follow the evolution of the ligand shell composition and morphology during the reaction. We observe the expected evolution in composition and we find that the ligand shell starts as a random mixture and gradually evolves towards a patchy morphology. When the composition has reached a plateau (i.e. when the reaction is generally assumed to be finished), the ligand shell morphology keeps evolving for days, slowly approaching its equilibrium configuration.