Conductive plastics: comparing alternative nanotechnologies by performance and life cycle release probability

Nanocomposites can be considered safe during their life cycle as long as the nanofillers remain embedded in the matrix. Therefore, a possible release of nanofillers has to be assessed before commercialization. This report addresses possible life cycle release scenarios for carbon nanotubes (CNT), graphene, and carbon black (CB) from a thermoplastic polyurethane (TPU) matrix. The content of each nanofiller was adjusted to achieve the same conductivity level. The nanofillers reduced the rate of nanoscale releases during mechanical processing with decreasing release in the order neat TPU, TPU-CNT, TPU-graphene, and TPU-CB. Released fragments were dominated by the polymer matrix with embedded or surface-protruding nanofillers. During electron microscopy analysis, free CB was observed, however, there was no free CNT or graphene. Quantitatively, the presence of free nanofillers remained below the detection limit of <0.01% of generated dust. Further, both the production process and type of mechanical processing showed a significant impact with higher release rates for injection-molded compared to extruded and sanded compared to drilled materials. Due to its optimal performance for further development, extruded TPU-CNT was investigated in a combined, stepwise worst case scenario (mechanical processing after weathering). After weathering by simulated sunlight and rain, CNT were visible at the surface of the nanocomposite; after additional sanding, fragments showed protruding CNT, but free CNT were not detected. In summary, this preliminary exposure assessment showed no indication that recommended occupational exposure limits for carbonaceous nanomaterials can be exceeded during the life cycle of the specific TPU nanocomposites and conditions investigated in this study.     

Indium solubility in iron studied with perturbed angular correlations

Segregation of In in Fe-based alloys containing 0.11–2.12 at.% In has been studied by measuring the perturbed angular correlations of γ-rays emitted in the nuclear decay of ¹¹¹In. The probe atoms were introduced into the alloys by either adding the carrier-free ¹¹¹In during melting or via ion implantation. Ageing of the samples at elevated temperatures followed by a slow cooling to room temperature allowed us to determine the upper limit of the solubility at room temperature, S(300 K)≤ 30 at. ppm. This value is far below the one reported in the published phase diagram. Quenching of the samples in water from 973–1373 K resulted in the determination of the indium solubility in iron at these elevated temperatures. This revised version was published online in August 2006 with corrections to the Cover Date.     

A specific heat and magnetization study of highT c ceramic superconductors

From the temperature dependence of the specific heat of the semiconductor La₂CuO₄ and the high temperature superconductors La_1.8Sr_0.2CuO₄ (T _c =37.2 K) and YBa_1.9K_0.1Cu₃O_6.9 (T _c =91.5 K) in the range 1.5–30 K, a strong similarity of the lowfrequency part of their phonon density of states with a peak around 10 meV could be inferred. In the case of La_1.8Sr_0.2CuO₄ the thermodynamical critical field belowT _c has been determined and using the Rutger's formula and the BCS model, a Sommerfeld coefficient γ=9 mJ·mol^?1 K^?1 was obtained, which, taking into account recent results of band structure calculations leads to an electron-phonon enhancement factor γ=1.3, value compatible withT _c =36 K when using McMillan's formula forT _c . A systematic study of the magnetization offered evidence for strong flux trapping effects at higher fields and for Meissner shielding by superconducting Josephson currents in fields below 6 mT at 4.2 K.     

Determination of elongational viscosity of polymer melts by RME and Rheotens experiments

Several linear (LLDPE, HDPE, PS) and long-chain-branched (LDPE, PP) polymer melts were investigated by an elongational rheometer (RME Rheometrics) and by Rheotens (Göttfert). The Molecular Stress Function (MSF) theory is briefly reviewed and used to extrapolate the steady-state elongational viscosity. To evaluate Rheotens experiments, a new process model is introduced which assumes that the elongational viscosity in the Rheotens test is a function of the draw ratio only. The apparent elongational viscosities extracted from Rheotens curves are found to lie in between the steady-state elongational viscosity and three times the shear viscosity.     

Nonlinear phenomena in contemporary vocal music.

Complex and multiphonic voice signals of vocal improvisors are analyzed within the framework of nonlinear dynamics. Evidence is given that nonlinear phenomena are extensively used by performers associated with contemporary music. Narrow-band spectrograms of complex vocalizations are used to visualize the appearance of nonlinear phenomena (spectral bifurcation diagrams). Possible production mechanisms are discussed in connection with previous research, personal performance and pedagogical experience. Examples for period doubling, biphonation and irregular aperiodic phonation in vocal sonorities of contemporary vocal improvisors are given, and glottal whistle production encompassed with biphonation and triphonation is shown. Furthermore, coincidences of harmonics-formant matching associated with abrupt transitions to subharmonics and biphonation in the vocal output are provided. This also shows the recurrent use of nonlinear phenomena by performers. It is argued that mechanisms such as source-tract coupling or vocal fold desynchronization due to asymmetry are used in a reproducible way for musical tasks.     

Übergangsmetall—methylen-komplexe: XLVIII. Addition und ringschluss bei reaktionen von α-ketodiazoalkanen mit metall—metall-doppelbindungen der metallcarbonyl-reihe: Aufbau metallacyclischer strukturen

The α-diazoketones 2a–h,k,l react with the dinuclear organorhodium complex 1 with elimination of dinitrogen and concomitant addition of their carbonyl-flanked carbene moieties upon the metal—metal double bond. The μ-alkylidene complexes 3f–h thus accessible, represent the final products; the trimethylsilyl derivative 3i was synthesized for comparison. By contrast, the derivatives 3a–e,l behave rather as IR-spectroscopically identified intermediates that, at room temperature, undergo rapid consecutive intramolecular cycloaddition reactions yielding the novel compounds 4a–e and 5l, respectively. Formation of 4a–e results from nucleophilic attack of the keto groups of the bridging ligands upon one of the metal carbonyl units. This type of cyclization process comprises the construction of a new oxygen—carbon bond. The metallacyclic structures thus obtained have been elucidated in the cases of 4c and 4e by means of single crystal X-ray diffraction techniques and no longer obey the structural criteria of type-3 μ-alkylidene complexes. An internal experiment concurrently carried out by use of the diazoalkane 2e furnished proof that the cyclization process occurred regiospecifically: only the more nucleophilic keto-oxygen atom is subject to ring closure, whereas the oxygen atom of the ester carbonyl group does not participate in this reaction. The bis(acyl)methylene derivatives 3f–h resist cyclization and retain their structures even at elevated temperatures (cf. boiling tetrahydrofuran). The carbocyclic diazo precursor 2k (diazodimedone) requires more drastic conditions (boiling benzene) for the reaction with compound 1 to occur; here, the cycloadduct 5k is formed following nitrogen elimination. According to a single crystal X-ray diffraction study, the ketocarbene fragment derived from 2k has been added across the dinuclear metalcarbonyl core, finally acting as a bridging structural unit. In contrast to the cycloadducts 4a–e, a new carbon—carbon bond is formed during the synthesis of 5k. The dimetallacycle 5l results from a two-step cyclo-elimination between the bisdiazoalkane 2l and the organorhodium compound 1.