Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Graphical operations on projective spaces

Motivated by the work of Crapo and Rota [6] on the lifting of a projective complex, we introduce a class of invariant operations associated to integral-weighted graphs, which we call graphical operations. Such operations generalize the sixth harmonic of a quadranguler set on a projective line. We determine the expansion of the graphical operations in terms of multi-linear bracket polynomials in a Grassmann-Cayley algebra. Reducibility and compositions of such invariant operations are also investigated with a number of examples.Supported by Courant Instructorship, New York University.     

An alternative for moduli stabilisation

The one-loop vacuum energy is explicitly computed for a class of perturbative string vacua where supersymmetry is spontaneously broken by a T-duality invariant asymmetric Scherk–Schwarz deformation. The low-lying spectrum is tachyon-free for any value of the compactification radii and thus no Hagedorn-like phase-transition takes place. Indeed, the induced effective potential is free of divergence, and has a global anti-de Sitter minimum where geometric moduli are naturally stabilised.     

Composting and biodegradation of thermally processed feather keratin polymer

Proteins obtained from agricultural sources represent a unique feedstock from which to prepare thermally processable polymers. In this study, thermally processed feather keratin films were composted with three-month-old compost inoculum in self-heating laboratory composters for 30 days and temperature and carbon dioxide development monitored. About 24% of the available carbon in the feather keratin polymer (FKP) was metabolized in this time and this may not be high enough for some applications. Degradation of the feather keratin polymers was observed within 10 days with concurrent molecular weight reduction measured using FT-IR. Visual inspection of the polymers also showed destruction of the films. A change in crystallinity was observed in DSC analysis and some degradation processes could be inferred from this as well.     

Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Excess enthalpies of aqueous ternary solutions of urea and polyols at 25°C

The heats of dilution of nine ternary solutions of urea and polyols have been determined at 25°C. Excess enthalpies and their virial coefficients h _xy have been evaluated and compared with the data reported in the literature for mono- and polyfunctional alcohols and other oxygenated nonelectrolytes. The group additivity approach of Savage and Wood was applied and the contributions to the enthalpy coefficients, due to the water mediated interactions between urea and the functional groups –CH₂–, –OH, and –O– were determined. On the other hand, by using empirical combination rules among the cross- and self-enthalpic interaction coefficients it is possible to emphasize the large differences in the behavior (even in the presence of urea) of the polyols (and in particular of cyclitols) and of saccharides.     

Intramolecular cyclization of acyl radicals onto the azido group: a new radical approach to cyclized lactams

[reaction: see text] Aryl- and alkyl-derived azidoacyl radicals, generated from thiolesters by intramolecular homolytic substitution at the sulfur, can undergo five- and six-membered cyclization onto the azido moiety to give cyclized lactams.